CN106984261A - A kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application - Google Patents
A kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application Download PDFInfo
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- CN106984261A CN106984261A CN201710344173.9A CN201710344173A CN106984261A CN 106984261 A CN106984261 A CN 106984261A CN 201710344173 A CN201710344173 A CN 201710344173A CN 106984261 A CN106984261 A CN 106984261A
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 52
- 229910002518 CoFe2O4 Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 22
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 229960003638 dopamine Drugs 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000536 complexating effect Effects 0.000 claims abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- -1 hydrogen salt Chemical class 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 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 description 1
- 241000549556 Nanos Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001483 mobilizing effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- B01J35/33—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- 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
Abstract
The invention discloses a kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application, the nanosphere is with SiO2Nanosphere is template, dopamine is generated polymeric shell layer in template with cobalt, iron metal ion complexing under conditions of pH8 9, is formed after carbonization annealing and be loaded with CoFe2O4The nitrogen-doped carbon material of metal nanoparticle, finally removes SiO with highly basic2Template is prepared into CoFe2O4/ N/C hollow nano-spheres.The present invention is with SiO2Nanoparticle, with larger specific surface area and porosity, improves the CoFe that shell is loaded to sacrifice the N/C matrix hollow-core constructions made by template2O4The distribution of nano metal particles, enhances the absorption to Organic Pollutants in Wastewater and catalytic activity, has widened using pH scopes, and is recycled because its magnetic is recyclable, economizes on resources.
Description
(1) technical field
The present invention relates to wastewater treatment and environmental catalysis technical field, and in particular to a kind of CoFe2O4/ N/C hollow nano-spheres
The preparation method and application of the heterogeneous class fenton catalyst of type.
(2) background technology
High-level oxidation technology can overcome traditional handicraft to be difficult to effectively handle difficult degradation as a kind of new water technology
The problem of organic matter, thus be widely studied.In recent years, based on potentiometric titrations (SO4 ●-) high-level oxidation technology turn into new
Study hotspot, compared to OH●, SO4 ●-With longer half-life period, which enhance the contact between free radical and pollutant, have
Beneficial to its degraded to pollutant.Meanwhile, SO4 ●-Have and OH●Close high redox potential (2.5-3.1V), or even
Also there is very strong activity, therefore energy efficient oxidation degradable organic pollutant, with good application under neutral and alkalescence condition
Prospect.
The activation of permonosulphuric acid hydrogen salt (PMS) is to produce SO4 ●-Major way, research shows, transition metal or transition gold
Belong to oxide nano particles heterogeneous catalysis decomposed P MS and produce SO4 ●-With very high efficiency, but individually nano particle due to
Its higher surface energy, inactivation of easily reuniting in aqueous, and metal ion easily leach and cause secondary pollution, therefore usually
Suitable carrier material is needed to load nano particle to improve its stability.In numerous materials, common carrier material is such as
Silica, activated carbon, graphene, titanium dioxide etc. are because it is to based on the chemical lazy of potentiometric titrations high-level oxidation technology
Property and be only capable of providing limited performance improvement, the requirement of actual use can not be met well, therefore, should be designed activity
Component is with being provided simultaneously with the advanced composite material (ACM) that the carrier of PMS mobilizing functions is combined, further to adjust and improve reactivity
Energy.
(3) content of the invention
Mesh of the present invention solves the bad mechanical strength of existing heterogeneous class fenton catalyst, pH and requires strict, metal ion
Leaching content is big, catalytic efficiency is not high and catalyst is difficult to the technical problem of recycling, so as to provide a kind of CoFe2O4/N/
C hollow Nano ball-type catalyst, and can be coupled with peroxy-monosulfate to be formed heterogeneous Fenton-like catalysis oxidation remove it is organic
Pollutant.
The technical solution adopted by the present invention is：
The present invention provides a kind of CoFe2O4/ N/C hollow nano-spheres, the nanosphere is with SiO2Nanosphere (particle diameter 100-
It is 200nm) template, dopamine is generated polymer shell in template with cobalt, iron metal ion complexing under conditions of pH8-9
Layer, forms after carbonization annealing and is loaded with CoFe2O4The nitrogen-doped carbon material of metal nanoparticle, finally removes SiO with highly basic2Mould
Plate is prepared into CoFe2O4/ N/C hollow nano-spheres.
Further, the polymeric shell layer is prepared as follows：By SiO2Nanosphere is added in deionized water a, is surpassed
Sound adds dopamine, Co (NO after mixing3)2·6H2O and FeCl2·4H2O, adjusts pH to 8.0~9.0, and fierceness is stirred at room temperature
Mix, centrifuge, precipitation is dried in vacuo after being washed with deionized water b, obtain the nanosphere that polymeric shell layer is generated in template；It is described
SiO2Nanosphere and dopamine, Co (NO3)2·6H2O and FeCl2·4H2O mass ratio is 1：0.87~1.1：0.06~0.18：
0.12~0.2；The deionized water a volumetric usages are with SiO2Nanometer ball weight is calculated as 1~1.3ml/g；The deionized water a and
Deionized water b is deionized water, is named for the ease of statement different step consumption difference, letter itself is without implication.
Further, the carbonization annealing conditions is are warming up to 700~800 DEG C with 3 DEG C/min heating rate, and keep
1.5~2.5h, obtains nitrogen-doped carbon material.
Further, the template minimizing technology is：By the nitrogen-doped carbon material and 1.5~2mol/L sodium hydroxides after carbonization
The aqueous solution or the mixing of mass concentration 25-28% ammoniacal liquor, SiO is removed in 70~90 DEG C of reactions2Nanometer ball template, centrifuges, washs, very
Sky is dried, and the CoFe is made2O4/ N/C hollow nano-spheres.
The present invention also provides a kind of CoFe2O4The preparation method of/N/C hollow nano-spheres, methods described is：(1) will
SiO2Nanosphere is added in deionized water a, and ultrasound adds dopamine, Co (NO after mixing3)2·6H2O and FeCl2·4H2O, is adjusted
PH to 8.0~9.0 is saved, at room temperature high degree of agitation (rotating speed 1300rpm, 16-20h), centrifugation, precipitation is washed with deionized water b
After be dried in vacuo, obtain Surface Creation polymeric shell layer nanosphere；The SiO2Nanosphere and dopamine, Co (NO3)2·
6H2O and FeCl2·4H2O mass ratio is 1：0.87~1.1：0.06~0.18：0.12~0.2；The deionized water a volumes
Consumption is with SiO2Nanometer ball weight is calculated as 1~1.3ml/g；
(2) by the nanosphere of step (1) Surface Creation polymeric shell layer in argon gas protects atmosphere, with 3 DEG C/min liter
Warm speed is warming up to 700~800 DEG C, and keeps 1.5~2.5h carbonization annealing, the material after being carbonized；
(3) material and 1.5~2mol/L sodium hydrate aqueous solutions or mass concentration 25-28% after step (2) is carbonized
Ammoniacal liquor is mixed, and SiO is removed in 70~90 DEG C of reactions2Nanometer ball template, centrifugation, washing, vacuum drying, is made the CoFe2O4/
N/C hollow nano-spheres.
Further, step (3) washing is to use volume ratio 1:1 ethanol and the mixed solution of deionized water are washed 3~5 times.
The present invention provides a kind of CoFe2O4Application of/N/C the hollow nano-spheres in degradable organic pollutant.
Further, the organic pollution be containing 1~100mg/L methylene blues, 1~100mg/L Norfloxacins or 1~
The waste water of 100mg/L phenol.
Further, the application is：By CoFe2O4/ N/C hollow nano-spheres are added containing organic pollution as catalyst
In waste water, permonosulphuric acid hydrogen salt is added, 25 DEG C, oscillating reactions under 250rpm realize the degraded of organic pollution, reaction terminates
Afterwards, by reaction solution Magnetic Isolation, collection catalyst is recycled；The content of the Organic Pollutants in Wastewater is 1-100mg/L,
The CoFe2O4/ N/C hollow nano-spheres consumption is calculated as 0.08~0.15g/L, the CoFe with wastewater volume2O4/ N/C is hollow to be received
Rice ball is 1 with permonosulphuric acid hydrogen salt weight ratio：6~8.
Further, pH value is adjusted to 2.0~10.0 after the addition permonosulphuric acid hydrogen salt.
SiO of the present invention2Nanosphere is prepared as follows：Tetraethyl orthosilicate, ethanol, deionized water and quality is dense
The mixing of 25-28% ammoniacal liquor is spent, at room temperature high degree of agitation, centrifugation takes precipitation to be washed and be dried in vacuo with ethanol, obtains SiO2Receive
Rice ball；The tetraethyl orthosilicate is 1 with ethanol, deionized water and ammoniacal liquor volume ratio：38.5~42.3：1.2~2.7：1.2~
2.7。
The CoFe of the present invention2O4The heterogeneous class fenton catalyst of/N/C hollow Nano ball-types is a kind of magnetic nanometer of tool
Level catalyst, the catalyst as sewage disposal.Such as processing contains phenol, antibiotic, dye class waste water.
The present invention is with SiO2Nanoparticle is sacrifices the N/C matrix hollow-core constructions made by template, with larger ratio table
Area and porosity, improve the CoFe that shell is loaded2O4The distribution of nano metal particles, is enhanced to organic dirt in waste water
Absorption and the catalytic activity of thing are contaminated, has been widened using pH scopes, and is recycled because its magnetic is recyclable, is economized on resources.
Compared with existing class Fenton type catalyst, main advantages of the present invention are as follows：
(1) CoFe of synthesis2O4/ N/C hollow nano-spheres are hollow mesoporous type spheric granules, and particle diameter reaches nanoscale, is
200~250nm, specific surface area is big, and suction-operated is strong, is conducive to active component fully to be contacted with oxidant, greatly improves catalysis
Efficiency.
(2) the iron cobalt dual-metal form in the present invention is the ferrite compounds CoFe of spinel-type2O4, structural property is steady
Fixed, metal ion is difficult dissolution, it is to avoid causes have certain synergy between secondary pollution, and iron cobalt dual-metal, is conducive to
Reaction is promoted to carry out.
(3) the heterogeneous class fenton catalyst of synthesis still remains higher catalytic activity in the range of pH 2~10, has
There are wider pH applications.
(4) catalyst of the invention has stronger magnetic, collects and reclaims easily in the presence of external magnet, is conducive to two
It is secondary to utilize, economize on resources.
(4) illustrate
Fig. 1 is CoFe made from embodiment 12O4The XRD of/N/C catalyst.
Fig. 2 is CoFe made from embodiment 12O4The SEM figures of/N/C catalyst, a is CoFe2O4The overall shape of/N/C materials
Looks figure, b is proof CoFe2O4/ N/C has the scanning electron microscope (SEM) photograph of hollow-core construction.
Fig. 3 is CoFe made from embodiment 12O4The photo that/N/C catalyst is separated under external magnet effect with reaction solution,
A is the solution cloudy state after catalytic reaction terminates, and b is the phenomenon that catalyst is separated with reaction solution under external magnet effect.
Fig. 4 is CoFe made from embodiment 12O4The dynamic curve diagram of/N/C catalyst degradation methylene blues.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：CoFe2O4/ N/C hollow nano-spheres
(1)SiO2The preparation of nanoparticle：By 2.6mL tetraethyl orthosilicates, 108mL ethanol, 5mL deionized waters, 5mL ammoniacal liquor
(mass concentration 25%) is added in conical flask, at room temperature high degree of agitation 12h, is centrifuged, is washed with ethanol 3~5 times, 80 DEG C true
Sky is dried, and obtains SiO2Nanoparticle 400mg, particle diameter 150nm.
(2) by 150mg SiO2Nanoparticle is added in 150mL deionized waters, and 150mg dopamines are added after ultrasound,
17.5mg Co(NO3)2·6H2O and 23.88mg FeCl2·4H2O, is 8.5 with Tris-HCl buffer solutions regulation pH, starts anti-
Should, mechanical agitation 18h, rotating speed 1300rpm, are collected by centrifugation black precipitate at room temperature, are washed with deionized after 2~3 times
80 DEG C of vacuum drying, obtain black particle thing 234mg.
(3) the black particle thing of gained in step (2) is put into be carbonized in the tube furnace of argon gas protection atmosphere and annealed, heating
Program keeps 2h to be warming up to 750 DEG C with 3 DEG C/min heating rate, the material 153mg after being carbonized.
(4) the material 153mg after step (3) is carbonized is put into hydrothermal reaction kettle, adds 45ml, 2mol/L sodium hydroxide
The aqueous solution (or mass concentration 25-28% ammoniacal liquor), reacts 5h to remove SiO at 80 DEG C2Ethanol is used in nanometer ball template, centrifugation
With the mixed solution (1 of deionized water：1, v/v) wash 3~5 times, 80 DEG C of vacuum drying produce final product CoFe2O4/ N/C is empty
Heart nanosphere 41mg.XRD spectrum as shown in Figure 1, SEM photograph as shown in Figure 2, external magnet effect under, CoFe2O4/ N/C is empty
The photo that heart nanometer ball shape catalyst is separated with pollutant solution is as shown in Figure 3.
From figure 1 it appears that the CoFe of synthesis2O4/ N/C X-ray diffraction characteristic peak and CoFe2O4Standard card
(JCPDS 22-1086) coincide substantially, the CoFe of this explanation synthesis2O4For cubic system spinel structure, and its main diffraction peak
All occur and relatively more sharp, show the CoFe of synthesis2O4Crystallinity is fine.
A can be seen that sample particle is spherical in shape from Fig. 2, and size is homogeneous, and its size is about 200nm, and b can from Fig. 2
Will become apparent from the hollow-core construction of the catalyst.
From figure 3, it can be seen that muddy reaction solution did not had a few minutes just to become in the presence of external magnet originally
Clarification, catalyst, in side, shows the CoFe by magnetic2O4/ N/C hollow Nano ball-type catalyst has good magnetic, favorably
Recycled in secondary recovery.
Embodiment 2：
The CoFe prepared with embodiment 12O4/ N/C hollow nano-spheres contain 20mg/L as the degraded of heterogeneous class fenton catalyst
The waste water of cationic dyes methylene blue.The degradation experiment is carried out in 250ml conical flasks, in 100ml waste water, catalyst
Dosage final concentration is calculated as 0.1g/L with wastewater volume, and permonosulphuric acid hydrogen salt (PMS) throwing amount is calculated as 0.8g/L with wastewater volume,
25 DEG C, oscillating reactions under 250rpm, make catalyst be well mixed with solution, reaction are taken out from reaction system every certain time
Liquid, determines methylene blue concentration with the change in reaction time, CoFe2O4The heterogeneous class fenton catalyst of/N/C hollow Nano ball-types
The result of degradation of methylene blue is as shown in Figure 4.Under similarity condition, using simulated wastewater+catalyst and simulated wastewater+PMS as control.
Figure 4, it is seen that only in the presence of PMS (no catalyst), there was only 10% methylene blue quilt in 20min
Remove, illustrate that the effect of PMS independent roles is extremely limited.When only under catalyst action, only 20% is sub- in reaction 20min
Methyl blue is removed, and this is mainly due to the suction-operated of the catalyst.And under the conditions of catalyst and PMS are simultaneous,
Methylene blue can be completely removed in 20min, and degradation effect has obtained significant raising, be shown in other conditions identical
In the case of, CoFe2O4The addition notable catalytic activation of/N/C hollow Nano ball-type catalyst PMS, a large amount of sulfate radicals of generation from
Accelerated to promote the degraded of methylene blue by base.
Embodiment 3
Catalytic activity test, its reaction condition ginseng are carried out using the material synthesized by step (3) in embodiment 1 as catalyst
Number and step are same as Example 2.As a result show, the methylene blue for there was only 52% in 20min is removed, and shows CoFe2O4/
The hollow configuration of N/C hollow Nano ball-type catalyst is played an important role, and substantially increases the catalytic degradation efficiency of catalyst.
Embodiment 4
Organic Pollutants in Wastewater in embodiment 2 is changed to 20mg/L antibiotic Norfloxacins by dyestuff methylene blue, its
His step and parameter are same as Example 2.As a result show, nearly 80% Norfloxacin is removed in 60min, is indicated
CoFe2O4The general applicability of/N/C hollow Nano ball-type catalyst.
Embodiment 5
Organic Pollutants in Wastewater in embodiment 2 is changed to 20mg/L phenol by dyestuff methylene blue, other steps and ginseng
Number is identical with specific embodiment 2.As a result show, phenol is completely removed in 20min, indicate CoFe2O4/ N/C hollow Nanos
The general applicability of ball shape catalyst.
Embodiment 6
The reacted reaction solution of embodiment 2 is separated with magnet, reacted catalyst is collected, 200W in ionized water is added
Ultrasonic 30min, continues to be washed with deionized after centrifuging 5min under 12000rpm, is dried in vacuo and collects at 80 DEG C, again
Utilize, carry out catalyst repeated experiment, other steps and parameter are same as Example 2.As a result find, carrying out 5 repetitions
Property experiment after, CoFe2O4/ N/C hollow Nano ball-type catalyst remains to reach 95% in 20min to the clearance of methylene blue
Left and right, indicates the catalyst remarkable stability and repeatability.
Embodiment 7
It is 2.1 by the reaction solution regulation pH in embodiment 2, other steps and parameter are identical with specific embodiment 2.As a result show
Show, nearly 96.2% methylene blue is removed in 20min, shows CoFe2O4/ N/C hollow Nano ball-type catalyst is in strong acid
Property under still have stronger activity.
Embodiment 8
It is 4.8 by the reaction solution regulation pH in embodiment 2, other steps and parameter are identical with specific embodiment 2.As a result show
Show, nearly 97.4% methylene blue is removed in 20min, shows CoFe2O4/ N/C hollow Nano ball-type catalyst is in acidity
Under the conditions of still keep stronger activity.
Embodiment 9
It is 6.3 by the reaction solution regulation pH in embodiment 2, other steps and parameter are identical with specific embodiment 2.As a result show
Show, nearly 96.1% methylene blue is removed in 20min, shows CoFe2O4/ N/C hollow Nano ball-type catalyst is in partially
Property under the conditions of still have stronger activity.
Embodiment 10
It is 9.1 by the reaction solution regulation pH in embodiment 2, other steps and parameter are identical with specific embodiment 2.As a result show
Show, nearly 99.04% methylene blue is removed in 20min, shows CoFe2O4/ N/C hollow Nano ball-type catalyst is in alkali
Property under have stronger activity.
The CoFe of table 12O4The Contrast on effect of the different pollutants of/N/C catalytic decomposition PMS degradeds
Claims (10)
1. a kind of CoFe2O4/ N/C hollow nano-spheres, it is characterised in that the nanosphere is with SiO2Nanosphere is template, in pH8-9
Under conditions of dopamine and cobalt, iron metal ion complexing is generated polymeric shell layer in template, form load after carbonization annealing
There is CoFe2O4The nitrogen-doped carbon material of metal nanoparticle, finally removes SiO with highly basic2Template is prepared into CoFe2O4/ N/C is hollow
Nanosphere.
2. CoFe as claimed in claim 12O4/ N/C hollow nano-spheres, it is characterised in that the polymeric shell layer is as follows
Prepare：By SiO2Nanosphere is added in deionized water a, and ultrasound adds dopamine, Co (NO after mixing3)2·6H2O and FeCl2·
4H2O, adjusts pH to 8.0~9.0, at room temperature high degree of agitation, centrifugation, and precipitation is dried in vacuo after being washed with deionized water b, is obtained
Obtain the nanosphere that polymeric shell layer is generated in template；The SiO2Nanosphere and dopamine, Co (NO3)2·6H2O and FeCl2·
4H2O mass ratio is 1：0.87~1.1：0.06~0.18：0.12~0.2；The deionized water a volumetric usages are with SiO2Nanometer
Ball weight is calculated as 1~1.3ml/g.
3. CoFe as claimed in claim 12O4/ N/C hollow nano-spheres, it is characterised in that the carbonization annealing conditions are：With 3 DEG C/
Min heating rate is warming up to 700~800 DEG C, and keeps 1.5~2.5h, obtains nitrogen-doped carbon material.
4. CoFe as claimed in claim 12O4/ N/C hollow nano-spheres, it is characterised in that the template minimizing technology is：Will carbonization
Nitrogen-doped carbon material afterwards is mixed with 1.5~2mol/L sodium hydrate aqueous solutions or mass concentration 25-28% ammoniacal liquor, 70~90
DEG C reaction remove SiO2Nanometer ball template, centrifugation, washing, vacuum drying, is made the CoFe2O4/ N/C hollow nano-spheres.
5. CoFe described in a kind of claim 12O4The preparation method of/N/C hollow nano-spheres, it is characterised in that methods described is：
(1) by SiO2Nanosphere is added in deionized water a, and ultrasound adds dopamine, Co (NO after mixing3)2·6H2O and FeCl2·
4H2O, adjusts pH to 8.0~9.0, at room temperature high degree of agitation, centrifugation, and precipitation is dried in vacuo after being washed with deionized water b, is obtained
Obtain the nanosphere of Surface Creation polymeric shell layer；The SiO2Nanosphere and dopamine, Co (NO3)2·6H2O and FeCl2·4H2O
Mass ratio be 1：0.87~1.1：0.06~0.18：0.12~0.2；The deionized water a volumetric usages are with SiO2Nanosphere
Weight is calculated as 1~1.3ml/g；
(2) by the nanosphere of step (1) Surface Creation polymeric shell layer in argon gas protects atmosphere, with 3 DEG C/min heating speed
Rate is warming up to 700~800 DEG C, and keeps 1.5~2.5h carbonization annealing, the material after being carbonized；
(3) material and 1.5~2mol/L sodium hydrate aqueous solutions or mass concentration 25-28% ammoniacal liquor after step (2) is carbonized
Mixing, SiO is removed in 70~90 DEG C of reactions2Nanometer ball template, centrifugation, washing, vacuum drying, is made the CoFe2O4/ N/C is empty
Heart nanosphere.
6. CoFe as claimed in claim 52O4The preparation method of/N/C hollow nano-spheres, it is characterised in that step (3) washing is to use
Volume ratio 1:1 ethanol and the mixed solution of deionized water are washed 3~5 times.
7. CoFe described in a kind of claim 12O4Application of/N/C the hollow nano-spheres in degradable organic pollutant.
8. application as claimed in claim 7, it is characterised in that the organic pollution is containing 1~100mg/L methylene blues, 1
The waste water of~100mg/L Norfloxacins or 1~100mg/L phenol.
9. application as claimed in claim 8, it is characterised in that the application is：By CoFe2O4/ N/C hollow nano-spheres are as urging
Agent is added in the waste water containing organic pollution, adds permonosulphuric acid hydrogen salt, and 25 DEG C, oscillating reactions under 250rpm, realization have
The degraded of organic pollutants, after reaction terminates, by reaction solution Magnetic Isolation, collection catalyst is recycled；The CoFe2O4/N/C
Hollow nano-sphere consumption is calculated as 0.08~0.15g/L, the CoFe with wastewater volume2O4/ N/C hollow nano-spheres and permonosulphuric acid
Hydrogen salt weight ratio is 1：6~8.
10. application as claimed in claim 9, it is characterised in that after the addition permonosulphuric acid hydrogen salt regulation pH value to 2.0~
10.0。
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