CN114870883B - Hollow carbon-based Fe monoatomic catalyst and preparation method and application thereof - Google Patents
Hollow carbon-based Fe monoatomic catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114870883B CN114870883B CN202210669068.3A CN202210669068A CN114870883B CN 114870883 B CN114870883 B CN 114870883B CN 202210669068 A CN202210669068 A CN 202210669068A CN 114870883 B CN114870883 B CN 114870883B
- Authority
- CN
- China
- Prior art keywords
- sio
- catalyst
- pof
- monoatomic
- hollow carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 230000002776 aggregation Effects 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 31
- 239000013309 porous organic framework Substances 0.000 claims description 23
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 230000005012 migration Effects 0.000 claims description 7
- 238000013508 migration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 150000004032 porphyrins Chemical class 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 13
- 238000009303 advanced oxidation process reaction Methods 0.000 description 6
- 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 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hollow carbon-based Fe monoatomic catalyst, a preparation method and application thereof, wherein a double-template protection strategy is adopted, a covalent organic framework is used as a carbon-based precursor to fix Fe ions, and the carbon-based Fe monoatomic catalyst with a hollow structure is synthesized by heat treatment under the limit of an inner template and an outer template. The double-template protection strategy not only can realize the hollow morphology structure of the catalyst, is beneficial to complete exposure of metal active centers and mass transfer of reaction substrates, but also can effectively inhibit metal center agglomeration and carbon layer coverage caused by thermal driving in the catalyst preparation process, and effectively improve the catalytic performance of the catalyst. The persulfate activation and pollutant degradation experiments show that Fe-N-C can efficiently activate monopersulfate and degrade organic pollutants, and has high stability and recycling characteristics. The catalyst has the advantages of simple preparation process, good catalytic effect, high stability of a catalytic system, low requirements on a treatment process and treatment equipment, and no secondary pollution.
Description
Technical Field
The invention belongs to the field of material preparation and organic wastewater advanced treatment, and particularly relates to a hollow carbon-based Fe monoatomic catalyst and a preparation method and application thereof.
Background
The rapid development of economy brings people with a good life and also derives a series of environmental problems. The problem of water pollution is particularly prominent in the environmental field. Numerous toxic and harmful organic pollutants, especially emerging organic pollutants, enter a water body and are not easy to decompose, so that serious threat is caused to ecological environment and human health. In recent years, advanced oxidation technology (PS-AOPs) using persulfate as oxidant can generate SO in the system 4 · - 、·OH、O 2 · - And 1 O 2 such oxygen-containing reactive species are considered to be one of the most advanced wastewater advanced treatment technologies for removing organic contaminants. In addition, compared with the conventional hydrogen peroxide advanced oxidation technology (H 2 O 2 AOPs), persulfates in PS-AOPs are not only convenient for storage and transportation, but also inexpensive and readily available and favored by environmental workers. But the key point for realizing the advanced treatment of wastewater by a high-efficiency PS-AOPs system is to effectively activate persulfate. Currently, a large number of catalysts have been developed for activating persulfates, such as homogeneous Co 2+ 、Fe 2+ 、Ag + And Co out of phase 2 O 3 、Fe 2 O 3 Etc. Although these catalysts can achieve persulfate activation under specific conditions, they have problems of low metal utilization, poor activation efficiency, or low catalyst recycling property and poor stability. Based on this, there is a need to develop a highly efficient and stable catalyst to activate persulfate to achieve the problem of PS-AOPs wastewater treatment.
Monoatomic catalysts (SACs) have become a new feature in the field of catalysis due to the characteristics of high metal utilization rate, easily-adjustable composition structure and the like. In particular, fe monoatomic catalysts exhibit great potential in persulfate activation reactions. Most of the monoatomic catalysts are currently prepared by direct pyrolysis of carbon-containing precursors. Although the pyrolysis synthesis method is simple and easy to operate, the developed monoatomic catalyst often suffers from problems of amorphous carbon layer coverage, metal center agglomeration and the like in the preparation process, so that the overall effect of persulfate activation is poor and the pollutant degradation performance is poor. Therefore, to obtain efficient monoatomically activated PS-AOPs degradation organic contaminant systems, new methods for monoatomic catalyst preparation are urgently developed.
Disclosure of Invention
The invention aims to provide a hollow carbon-based Fe monoatomic catalyst, a preparation method thereof and application of directionally activating persulfate to degrade organic pollutants, aiming at the defects of the existing monoatomic catalyst preparation technology. The invention adopts a double-template protection strategy, takes a covalent organic framework as a carbon-based precursor to fix Fe ions, and synthesizes the carbon-based Fe single-atom catalyst (Fe-N-C) with a hollow structure by heat treatment under the limit of an inner template and an outer template. The persulfate activation and pollutant degradation experiments show that Fe-N-C can efficiently activate persulfate and degrade organic pollutants, and has high stability and recycling property. The catalyst disclosed by the invention is simple in preparation process, good in catalytic effect, high in stability of a catalytic system and great in application potential.
In order to achieve the above purpose, the invention adopts the following technical scheme: a hollow carbon-based Fe monoatomic catalyst is characterized in that: the hollow carbon-based Fe monoatomic catalyst is marked as follows: fe-N-C is prepared by taking a porphyrin-based covalent organic framework as a carbon-based precursor carrier to anchor an Fe component and combining an internal and external double-template domain-limiting strategy with a calcination method.
The preparation method adopted by the invention not only can form a hollow spherical structure by the shape of the genetic template, but also can prevent migration of Fe species and masking of a carbon layer on the surface under heat treatment, thereby being beneficial to maintaining monoatomic physicochemical characteristics, exposing more metal active sites and improving the efficiency of activating persulfate to degrade organic pollutants.
The invention adopts the following another technical scheme: a preparation method of a hollow carbon-based Fe monoatomic catalyst is characterized by comprising the following steps of: the method comprises the following steps:
1) To prepare hollow covalent organic framework supports, aminated silica microspheres (SiO 2 -NH 2 ) As a core, uniformly dispersed in an acetic acid solution, and then p-phthalaldehyde was added dropwise theretoAnd pyrrole, partial terephthalaldehyde and SiO under acidic conditions 2 -NH 2 Performing aldehyde-amine condensation, adding trifluoroacetic acid catalyst and nitrobenzene oxidant into the above solution, heating to obtain pyrrole and terephthalaldehyde on SiO 2 -NH 2 The covalent organic framework is polymerized on the surface, and the solid obtained after filtration, washing and drying is marked as POF@SiO 2 。
2) The POF@SiO is prepared 2 Dispersing in N, N-dimethylformamide solution, ultrasonic forming into uniform suspension, adding FeCl 2 ·4H 2 Refluxing O monoatomic precursor in oil bath to fix Fe on POF@SiO 2 In the process, the solid is marked as Fe/POF@SiO after being coordinated with N atoms in a covalent organic framework and filtered 2 。
3) In order to prevent migration of the immobilized Fe component during subsequent calcination and aggregation and coverage of the covalent organic framework during carbonization, the Fe/POF@SiO is prepared by 2 Redispersing in alcohol solution containing ammonia water, then dropping ethyl orthosilicate, stirring to make Fe/POF@SiO 2 SiO formation on the surface 2 Coating to inhibit migration of Fe component and covalent organic framework carrier, filtering, washing and drying to obtain solid, denoted as SiO 2 @Fe/POF@SiO 2 。
4) Under the condition of nitrogen, the SiO obtained above is treated 2 @Fe/POF@SiO 2 Calcining at high temperature to form ordered coordination structure between Fe and N atoms, soaking in dilute hydrofluoric acid solution, and etching SiO 2 And (3) preparing an inner template and an outer template, manufacturing a hollow carbon-based Fe single-atom catalyst, washing and drying, and marking as Fe-N-C.
Wherein, the adding amount of terephthalaldehyde in the step 1) is 40-60 mg, the adding amount of pyrrole is 40-60 mu L, the amount of trifluoroacetic acid is 200 mu L, and the amount of nitrobenzene is 1.0mL.
Wherein FeCl in step 2) 2 ·4H 2 The amount of O is 150-250mg, and the reflux temperature is 120-150 ℃.
Wherein the concentration of the ammonia water in the step 3) is 1v/v%.
Wherein, the temperature is 600-900 ℃ and nitrogen is used in the high-temperature calcination in the step 4)The air flow rate is 20-60 mL.min -1 The concentration of the hydrofluoric acid dilute solution is 10-30wt%.
The application of the hollow carbon-based Fe monoatomic catalyst is as follows: for activating the peroxymonosulfate and degrading organic contaminants.
According to the hollow carbon-based Fe monoatomic catalyst, a double-template protection strategy is adopted, a covalent organic framework is used as a carbon-based precursor to fix Fe ions, and the carbon-based Fe monoatomic catalyst (Fe-N-C) with a hollow structure is synthesized by heat treatment under the limit of an inner template and an outer template. The method not only inhibits the migration of Fe species on the surface in the heat treatment process, but also exposes more metal active sites, which is beneficial to mass transfer of reaction substrates, thereby effectively improving the efficiency of activating persulfate to degrade organic pollutants. At present, the hollow carbon-based Fe monoatomic catalyst prepared by the method is not reported for activating persulfate to degrade organic pollutants.
The invention has the remarkable advantages that: (1) According to the invention, a dual-template protection strategy is adopted for the first time, a porphyrin-based covalent organic framework is used as a carbon-based precursor to fix Fe ions, and migration of Fe species on the surface and masking of a carbon layer under heat treatment can be effectively prevented under the limiting field of the dual-template, so that the single-atom physical and chemical characteristics are maintained, more metal active sites are exposed, and the catalytic activity is improved. The catalyst disclosed by the invention is simple in preparation process, good in reproducibility, favorable for large-scale popularization and wide in application prospect. (2) The carbon-based Fe monoatomic catalyst (Fe-N-C) synthesized by the method has a hollow morphology structure, has large specific surface area, is beneficial to full exposure of metal active sites and mass transfer of catalytic substrates, and is beneficial to improving catalytic performance. (3) The catalyst disclosed by the invention is simple in preparation process, good in catalytic effect, high in stability of a catalytic system, favorable for large-scale popularization and wide in application prospect.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an XRD pattern of Fe-N-C of the present invention.
FIG. 2 is a TEM image (a), HRTEM image (b), spherical aberration electron microscope STEM image (C), dark field scanning element distribution diagram (d-g) of Fe-N-C of the present invention.
FIG. 3 is a graph showing the degradation activity of p-nitrophenol (4-NP) of the present invention, wherein (a) is the addition of PMS alone, (b) is the addition of Fe-N-C alone, (C) is the addition of N-C and PMS, and (d) is the addition of Fe-N-C and PMS.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Comparative example 1
The preparation of the N-C catalyst comprises the following steps: 400mgSiO 2 -NH 2 Uniformly dispersing in 250mL acetic acid solution, adding 50mg terephthalaldehyde and 52.4 mu L pyrrole, performing ultrasonic treatment for 30min, adding 200 mu L trifluoroacetic acid and 1mL nitrobenzene into the solution, heating to 80deg.C, stirring for 12 hr, filtering, washing, and drying to obtain solid marked as POF@SiO 2 ；
POF@SiO 2 Redispersing in 100mL ethanol solution added with 3.4mL ammonia water, then rapidly dropping 12mL tetraethoxysilane, stirring for 5h, filtering, washing and drying to obtain solid, which is marked as SiO 2 @POF@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Under the condition of nitrogen, the SiO obtained above is treated 2 @POF@SiO 2 Heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, soaking the obtained solid in dilute hydrofluoric acid solution for 24 hours, and etching SiO 2 And (5) washing and drying the template to obtain the carbon-based catalyst, which is marked as N-C.
Example 1
The preparation of the Fe-N-C catalyst comprises the following steps: 200mg of the POF@SiO prepared above was reacted 2 Dispersing in 100mLN, N-dimethylformamide solution, ultrasonically forming uniform suspension, adding 200mg FeCl 2 ·4H 2 O, refluxing in an oil bath at 130 ℃ for 24 hours, filtering and washing, and the obtained solid is marked as Fe/POF@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Fe/POF@SiO 2 Redispersing in 100mL ethanol solution added with 3.4mL ammonia water, then rapidly dropping 12mL tetraethoxysilane, stirring for 5h, filtering, washing and drying to obtain solid, which is marked as SiO 2 @Fe/POF@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Under the condition of nitrogen, the SiO obtained above is treated 2 @Fe/POF@SiO 2 Heating to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours. Soaking in dilute hydrofluoric acid solution for 24 hr to etch SiO 2 And (3) washing and drying the template to obtain the hollow carbon-based Fe single-atom catalyst, which is marked as Fe-N-C. FIG. 1 shows the XRD pattern of Fe-N-C. It can be seen from the figure that the prepared Fe-N-C has a broad diffraction peak of carbon at 2θ=26°, and no peaks of Fe nanoparticles and Fe oxide were detected, indicating no aggregation of Fe nanoparticles. FIG. 2 shows the elemental distribution diagrams of TEM, HRTEM, spherical aberration correcting transmission electron microscope SETM and EDX of Fe-N-C, respectively. From the TEM image, it can be seen that Fe-N-C has a hollow spherical structure. The presence of Fe-containing nanoparticles was not observed from the HRTEM images. In the EDX element profile we found that the presence of Fe element was detected in addition to C, N element. From the SETM diagram we further confirm the presence of Fe, and Fe is anchored to the carbon material surface in the form of a single atom.
Example 2
Degradation Properties of 4-NP
The prepared catalyst is used for activating the persulfate to degrade 4-NP, specifically, 10mg of Fe-N-C catalyst is weighed and dispersed in 50mL of water solution containing 30mg/L of p-chloronitrobenzene 4-NP, the mixture is stirred uniformly, 1.5mmol/L of sodium persulfate is added, sampling is carried out at fixed time, and after filtration by a disposable filter head, the concentration of residual 4-NP is detected at 317nm by an ultraviolet spectrophotometer. The degradation efficiency is shown in FIG. 3, and it can be seen that 4-NP is hardly degraded when sodium persulfate is added. When only Fe-N-C is added, the removal of 4-NP is only 32% and does not change along with the reaction time, which indicates that the pure Fe-N-C material only has an adsorption effect on 4-NP. However, when the sodium persulfate is added in the presence of the Fe-N-C, the degradation effect of the 4-NP is obviously improved, and the degradation efficiency is up to 98% in 10min, which indicates that the Fe-N-C can activate the sodium persulfate to almost completely degrade the 4-NP. When the N-C is used to replace Fe-N-C activated persulfate, the degradation efficiency of 4-NP is only 26%, which indicates that the Fe component plays a key role in the process of activating persulfate. The experimental result shows that the Fe-N-C catalyst has high-efficiency performance of activating persulfate to degrade 4-NP.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. A preparation method of a hollow carbon-based Fe monoatomic catalyst is characterized by comprising the following steps of: the hollow carbon-based Fe monoatomic catalyst is marked as follows: fe-N-C is prepared by taking a porphyrin-based covalent organic framework as a carbon-based precursor carrier to anchor an Fe component and combining an internal and external double-template domain-limiting strategy with a calcination method; the preparation method of the hollow carbon-based Fe monoatomic catalyst comprises the following steps:
1) To prepare hollow covalent organic framework supports, aminated silica microspheres (SiO 2 -NH 2 ) As a core, uniformly dispersed in acetic acid solution, then added dropwise with terephthalaldehyde and pyrrole, and under acidic condition, part of terephthalaldehyde and SiO 2 -NH 2 Performing aldehyde-amine condensation, adding trifluoroacetic acid catalyst and nitrobenzene oxidant into the above solution, heating to obtain pyrrole and terephthalaldehyde on SiO 2 -NH 2 The covalent organic framework is polymerized on the surface, and the solid obtained after filtration, washing and drying is marked as POF@SiO 2 ；
2) The POF@SiO is prepared 2 Dispersing in N, N-dimethylformamide solution, ultrasonic forming into uniform suspension, adding FeCl 2 ·4H 2 Refluxing O monoatomic precursor in oil bath to fix Fe on POF@SiO 2 In the process, the solid is marked as Fe/POF@SiO after being coordinated with N atoms in a covalent organic framework and filtered 2 ；
3) In order to prevent migration of the immobilized Fe component during subsequent calcination and aggregation and coverage of the covalent organic framework during carbonization, the Fe/POF@SiO is prepared by 2 Redispersing in alcohol solution containing ammonia water, then dropping ethyl orthosilicate, stirring to make Fe/POF@SiO 2 SiO formation on the surface 2 Coating to inhibit migration of Fe component and covalent organic framework carrier, filtering, washing and drying to obtain solid, denoted as SiO 2 @Fe/POF@SiO 2 ；
4) Under the condition of nitrogen, the SiO obtained above is treated 2 @Fe/POF@SiO 2 Calcining at high temperature to form ordered coordination structure between Fe and N atoms, soaking in dilute hydrofluoric acid solution, and etching SiO 2 And (3) preparing an inner template and an outer template, manufacturing a hollow carbon-based Fe single-atom catalyst, washing and drying, and marking as Fe-N-C.
2. The method for preparing the hollow carbon-based Fe monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the addition amount of terephthalaldehyde in the step 1) is 40-60 mg, the addition amount of pyrrole is 40-60 mu L, the amount of trifluoroacetic acid is 200 mu L, and the amount of nitrobenzene is 1.0mL.
3. The method for preparing the hollow carbon-based Fe monoatomic catalyst according to claim 1, wherein the method comprises the following steps: feCl in step 2) 2 ·4H 2 The amount of O is 150-250mg, and the reflux temperature is 120-150 ℃.
4. The method for preparing the hollow carbon-based Fe monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the concentration of ammonia in step 3) was 1v/v%.
5. The method for preparing the hollow carbon-based Fe monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the temperature is 600-900 ℃ and the nitrogen flow rate is 20-60 mL.min during the high-temperature calcination in the step 4) -1 The concentration of the hydrofluoric acid dilute solution is 10-30wt%.
6. The use of the preparation method of the hollow carbon-based Fe monoatomic catalyst according to claim 1, wherein: the hollow carbon-based Fe monoatomic catalyst is used for activating the peroxymonosulfate and degrading organic pollutants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210669068.3A CN114870883B (en) | 2022-06-14 | 2022-06-14 | Hollow carbon-based Fe monoatomic catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210669068.3A CN114870883B (en) | 2022-06-14 | 2022-06-14 | Hollow carbon-based Fe monoatomic catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114870883A CN114870883A (en) | 2022-08-09 |
| CN114870883B true CN114870883B (en) | 2023-08-18 |
Family
ID=82681980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210669068.3A Active CN114870883B (en) | 2022-06-14 | 2022-06-14 | Hollow carbon-based Fe monoatomic catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114870883B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116078431B (en) * | 2022-12-13 | 2024-06-14 | 湘潭大学 | Au-based catalytic material based on hollow TTI-COF and application of Au-based catalytic material in catalyzing reduction of 4-nitrophenol |
| CN115999610A (en) * | 2022-12-28 | 2023-04-25 | 陕西科技大学 | NC supported cementite AOP catalyst with unsaturated center and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109482235A (en) * | 2018-12-04 | 2019-03-19 | 合肥工业大学 | A kind of preparation method and applications of the metal nano catalyst of the doped meso-porous carbon load of N- |
| CN110170331A (en) * | 2019-06-14 | 2019-08-27 | 中国科学院长春应用化学研究所 | A kind of hollow porous carbon ball nano material of iron nitrogen codope and preparation method thereof |
| CN111013576A (en) * | 2019-12-25 | 2020-04-17 | 中南大学 | Monoatomic catalyst prepared based on surface immobilization method |
| CN111659444A (en) * | 2020-06-20 | 2020-09-15 | 珠海复旦创新研究院 | Carbon-based limited-area interface supported palladium single-atom catalyst and preparation method thereof |
| CN111952608A (en) * | 2020-07-21 | 2020-11-17 | 江苏大学 | Preparation method of monoatomic iron-based oxygen reduction catalyst |
| CN112973759A (en) * | 2021-03-10 | 2021-06-18 | 中国石油大学(华东) | Preparation method of metal monatomic catalyst, metal monatomic catalyst and application |
| CN113198511A (en) * | 2021-05-10 | 2021-08-03 | 南京大学 | Nitrogen-doped carbon-supported Fe-Co bimetallic single-atom catalyst for efficiently activating persulfate and preparation method thereof |
| CN113410579A (en) * | 2021-05-18 | 2021-09-17 | 北京化工大学 | Monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material and preparation method and application thereof |
| CN113663712A (en) * | 2021-09-16 | 2021-11-19 | 西华师范大学 | Efficient bimetallic OER catalyst derived based on double-template method and preparation method thereof |
| CN113680348A (en) * | 2021-08-26 | 2021-11-23 | 四川大学 | Preparation method, product and application of carbon-based single-atom catalyst for efficiently activating PMS |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841620B (en) * | 2020-06-23 | 2021-11-05 | 华南理工大学 | Millimeter-grade peroxymonosulfate activator ZSM-5- (C @ Fe) and preparation method and application thereof |
-
2022
- 2022-06-14 CN CN202210669068.3A patent/CN114870883B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109482235A (en) * | 2018-12-04 | 2019-03-19 | 合肥工业大学 | A kind of preparation method and applications of the metal nano catalyst of the doped meso-porous carbon load of N- |
| CN110170331A (en) * | 2019-06-14 | 2019-08-27 | 中国科学院长春应用化学研究所 | A kind of hollow porous carbon ball nano material of iron nitrogen codope and preparation method thereof |
| CN111013576A (en) * | 2019-12-25 | 2020-04-17 | 中南大学 | Monoatomic catalyst prepared based on surface immobilization method |
| CN111659444A (en) * | 2020-06-20 | 2020-09-15 | 珠海复旦创新研究院 | Carbon-based limited-area interface supported palladium single-atom catalyst and preparation method thereof |
| CN111952608A (en) * | 2020-07-21 | 2020-11-17 | 江苏大学 | Preparation method of monoatomic iron-based oxygen reduction catalyst |
| CN112973759A (en) * | 2021-03-10 | 2021-06-18 | 中国石油大学(华东) | Preparation method of metal monatomic catalyst, metal monatomic catalyst and application |
| CN113198511A (en) * | 2021-05-10 | 2021-08-03 | 南京大学 | Nitrogen-doped carbon-supported Fe-Co bimetallic single-atom catalyst for efficiently activating persulfate and preparation method thereof |
| CN113410579A (en) * | 2021-05-18 | 2021-09-17 | 北京化工大学 | Monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material and preparation method and application thereof |
| CN113680348A (en) * | 2021-08-26 | 2021-11-23 | 四川大学 | Preparation method, product and application of carbon-based single-atom catalyst for efficiently activating PMS |
| CN113663712A (en) * | 2021-09-16 | 2021-11-19 | 西华师范大学 | Efficient bimetallic OER catalyst derived based on double-template method and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electronic structure modulation of covalent organic frameworks by single-atom Fe doping for enhanced oxidation of aqueous contaminants;Yao Yunjin et al.;《CHEMICAL ENGINEERING SCIENCE》;第209卷;115211 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114870883A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114870883B (en) | Hollow carbon-based Fe monoatomic catalyst and preparation method and application thereof | |
| CN111790422B (en) | Graphitized nitrogen-complexed Fe (III) -Fe0Catalyst, and synthesis method and application thereof | |
| CN108499529B (en) | Active coke supported nano gold catalyst and preparation method and application thereof | |
| CN111054417B (en) | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof | |
| CN113477270B (en) | Preparation method of copper-iron bimetal confined nitrogen-doped carbon nano tube composite material | |
| CN113943030B (en) | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof | |
| CN111790386A (en) | Method for preparing catalyst by utilizing coagulated sludge of waterworks and application | |
| CN115400775B (en) | Carbon nitride supported bimetallic single-atom catalyst and preparation method and application thereof | |
| Saka | Metal-free hybrid composite particles with phosphorus and oxygen-doped graphitic carbon nitride dispersed on kaolin for catalytic activity toward efficient hydrogen release | |
| CN113210003A (en) | Preparation method of composite visible-light-driven photocatalyst graphene quantum dot/graphite-phase nitrogen carbide | |
| Feng et al. | Degradation of ofloxacin using peroxymonosulfate activated by nitrogen-rich graphitized carbon microspheres: Structure and performance controllable study | |
| Li et al. | Enhanced ozonation of pollutants by MgO nanoclusters/sewage sludge-derived hierarchical porous carbon: experimental and theoretical study | |
| Jalalat et al. | Anchoring modified g-C3N4 with Bi5O7Br: S-scheme photocatalysts with boosted activities in elimination of inorganic and organic pollutants | |
| CN115814829A (en) | Co and Mo 2 C-codoped biochar-based composite material and preparation method and application thereof | |
| CN113336310B (en) | Catalytic ozone water treatment method using cobalt-containing nitrogen-doped ordered mesoporous carbon as catalyst | |
| CN115715980A (en) | Mn 3 O 4 CNTs Fenton catalyst, preparation method and application thereof | |
| CN114643058A (en) | Ternary nano alloy catalyst for decomposing hydrogen peroxide to generate hydroxyl radicals to degrade organic wastewater and preparation method thereof | |
| Liang et al. | Growth of iron (hydr) oxides on different carbon substrates and their Fenton-like performance | |
| CN112871174A (en) | Preparation method and application of hexagonal flaky nano nickel oxide catalyst | |
| CN114471565B (en) | Preparation method and application of zero-valent copper modified and enhanced zero-valent iron-carbon micro-electrolysis material | |
| CN115090295B (en) | Fe (Fe) 3 O 4 /C/MnO 2 RGO material and preparation method and application thereof | |
| CN113145100B (en) | Preparation method of efficient graphene-based lanthanide nanocomposite | |
| CN115155596B (en) | Preparation method and application of three-dimensional cluster structure re-CuFeNi-MMOs nanocomposite | |
| CN114931954B (en) | Two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide, and preparation method and application thereof | |
| CN115007183B (en) | Preparation method of monoatomic transition metal/nitrogen doped mesoporous carbon material for producing nitrogen by electrocatalytic reduction of nitrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |