CN114713260B - N, S Co-doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC, preparation method and application thereof - Google Patents
N, S Co-doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC, preparation method and application thereof Download PDFInfo
- Publication number
- CN114713260B CN114713260B CN202210357568.3A CN202210357568A CN114713260B CN 114713260 B CN114713260 B CN 114713260B CN 202210357568 A CN202210357568 A CN 202210357568A CN 114713260 B CN114713260 B CN 114713260B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coo
- nsoc
- doped
- mof
- 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
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 4
- 102000020897 Formins Human genes 0.000 claims description 3
- 108091022623 Formins Proteins 0.000 claims description 3
- 229960005404 sulfamethoxazole Drugs 0.000 abstract description 26
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 abstract description 26
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 239000012621 metal-organic framework Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000012466 permeate Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000007885 magnetic separation Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 230000003746 surface roughness Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000006652 catabolic pathway Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 small molecule compound Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses Co/CoO/Co Co-doped with Co-MOF derivative N, S 9 S 8 An NSOC catalyst, a preparation method and application thereof, belonging to the technical field of metal organic framework derivative materials. The invention aims to solve the defects of high pollution cost, low degradation efficiency and the like of sulfamethoxazole in the existing water treatment, and the invention firstly uses a hydrothermal method to prepare Co-MOF containing N, S element, and then obtains N, S Co-doped catalyst by a calcination mode under a protective atmosphere. The surface of the catalyst prepared by the invention contains rich hydrophilic groups, which is beneficial to the dispersion effect in water; magnetic and can be recovered by magnetic separation; the surface roughness can increase the specific surface area of the catalyst; the catalyst has extremely strong hydrophilicity, and water drops can quickly permeate into the catalyst after contacting the catalyst, thereby being beneficial to improving the catalytic effect. Has very good activation effect on PMS, certain ion interference resistance, and higher recycling property and recycling stability.
Description
Technical Field
The invention belongs to the technical field of metal organic frame derivative materials.
Background
Many areas are now facing serious water pollution, where the problem of contamination with antibiotics is very serious. Antibiotics are chemically stable and poorly biodegradable, toxic, mutagenic and carcinogenic, and thus effective and economical techniques have been developed to deal withThese antibiotics are necessary. Peroxymonosulfate (PMS) catalysis offers the possibility to promote the reaction with small amounts of intermediates under mild conditions and is therefore a very efficient way of antibiotic degradation. The PMS-catalyzed degradation of antibiotics is essentially the generation of sulfate radicals (SO) by catalysts and PMS-catalyzed processes 4 ·— ) Hydroxyl radical (. OH), superoxide radical (O) 2 ·— ) Singlet oxygen 1 O 2 ) Is oxidized and decomposed into inorganic substances such as CO 2 、H 2 O, etc.
In recent years, metal organic framework Materials (MOFs) are widely used as efficient catalysts for CO due to various coordination modes and unique spatial structures 2 Reduction, hydrogen production, battery and degradation of organic pollutants. However, MOFs are not magnetic, and are difficult to separate from the solution after being directly used as a catalyst for degradation, so that the MOFs are attempted to form metal nano particles with certain magnetism through calcination, and meanwhile, the original framework of the MOFs is maintained, so that the formed carbon-coated metal nano particles are uniformly dispersed in the metal nano particles, the contact area between active sites and pollutants is increased, and the degradation efficiency is improved.
Disclosure of Invention
In order to solve the defects of high pollution cost, low degradation efficiency and the like of Sulfamethoxazole (SMX) in the existing water treatment, the invention aims to provide a preparation method and application of a N, S Co-doped catalyst obtained by calcining Co-MOF containing N, S element in a ligand.
The invention is realized by the following technical scheme:
n, S Co-doped Co/CoO/Co 9 S 8 The preparation method of the @ NSOC catalyst specifically comprises the following steps:
the preparation method comprises the following specific steps:
(1) Preparation of Co-MOF containing N, S element:
2.2 to 2.3mmol Co (CH) 3 COO) 2 ·4H 2 O, 2.4 to 2.5mmol of 2, 5-thiophenedicarboxylic acid (H) 2 tdc), and 2.8 to 2.9mmol of 4,4 '-bipyridine (4, 4' -bpy), dissolved in30mL of water; transferring the obtained mixture into a high-pressure reaction kettle, heating for 5-7 h at 128-132 ℃, and cooling to room temperature to obtain the Co-MOF with pink crystals containing N, S element.
(2) N, S doped Co/CoO/Co 9 S 8 Preparation of @ NSOC catalyst:
putting the Co-MOF containing N, S element prepared in the step (1) into a tube furnace, and under a protective atmosphere, keeping the temperature at 4-6 ℃ for min -1 Heating to 790-810 deg.C, maintaining for 2.5 hr or more, naturally cooling to room temperature to obtain Co/CoO/Co 9 S 8 @ NSOC catalyst.
Preferably, the Co (CH) in step (1) 3 COO) 2 ·4H 2 O:0.54g,2.27mmol, 2, 5-thiophenedicarboxylic acid: 0.42g,2.47mmol, and 4,4' -bipyridine: 0.444g,2.84mmol.
Preferably, the heating temperature in step (1) is 130 ℃.
Preferably, the heating time in step (1) is 6 hours.
Preferably, the rate of temperature increase in step (2) is 5℃min -1 。
Preferably, the holding temperature in the tube furnace in step (2) is 800 ℃.
Preferably, the holding time in the tube furnace in step (2) is 3 hours.
Preferably, in step (2) N is maintained in the muffle furnace 2 And (5) circulating.
Another object of the present invention is to provide a N, S Co-doped Co/CoO/Co 9 S 8 The application of the @ NSOC catalyst in the aspect of degrading SMX specifically comprises the following steps:
adding the catalyst and PMS into an SMX aqueous solution, wherein the concentration of the catalyst in the solution is 100mg/L, and the concentration of the PMS is 0.8mM;
preferably, the catalytic degradation temperature is 25 ℃.
The invention has the beneficial effects that:
compared with Co-MOF, the surface of the catalyst prepared by the invention contains rich hydrophilic groups, which is beneficial to the dispersion effect in water; has certain magnetism, and can be recovered by a magnetic separation mode after catalytic degradation is completed; the invention presents a flaky stacked state, has a rough surface and is full of small raised particles, and the structure can increase the specific surface area of the catalyst, thereby being beneficial to contact between pollutants and the catalyst; the catalyst has extremely strong hydrophilicity, and water drops can quickly permeate into the catalyst after contacting the catalyst, thereby being beneficial to improving the catalytic effect.
Tests show that the catalyst has very good activation effect on PMS, has certain ion interference resistance, can adapt to more complex environments, and also has higher recycling property and cycle stability.
Drawings
FIG. 1Co-MOF and Co/CoO/Co 9 S 8 XRD spectrum of @ NSOC;
FIG. 2 (a, b) Co/CoO/Co 9 S 8 SEM image of @ NSOC; (c) Co/CoO/Co 9 S 8 Mapping graph of @ NSOC;
FIG. 3 (a) Co/CoO/Co 9 S 8 TEM images of @ NSOC; (b) Co/CoO/Co 9 S 8 HRTEM images of @ NSOC;
FIG. 4Co/CoO/Co 9 S 8 FT-IR spectrogram of @ NSOC;
FIG. 5Co-MOF and Co/CoO/Co 9 S 8 Nitrogen adsorption isotherms for @ NSOC;
FIG. 6Co-MOF and Co/CoO/Co 9 S 8 Hysteresis loop of @ NSOC;
FIG. 7Co-MOF and Co/CoO/Co 9 S 8 Water contact angle of @ NSOC;
FIG. 8Co/CoO/Co 9 S 8 XPS of @ NSOC. Spectra of total spectrum (a), co 2p (b), O1S (C), C1S (d), S2 p (e), N3 d (f);
FIG. 9Co-MOF and Co/CoO/Co 9 S 8 Catalytic degradation curve (a) and first order kinetics curve (b) of @ NSOC versus SMX;
FIG. 10 effect of catalyst amount, PMS amount, pH and temperature on catalytic activity;
fig. 11 anti-ion interference experiment: (a) HCO (hydrogen chloride) 3 - ;(b)Cl - ;(c)HPO 4 2- The method comprises the steps of carrying out a first treatment on the surface of the (d) Effect of HA on SMX removal
FIG. 12 effect of real body of water on SMX removal;
FIG. 13Co/CoO/Co 9 S 8 Cycling experiments of catalytic degradation of SMX by activating PMS with NSOC;
FIG. 14Co/CoO/Co 9 S 8 XRD patterns before and after the catalytic degradation of SMX by the NSOC activated PMS;
FIG. 15Co/CoO/Co 9 S 8 Active species capture experiments for catalytic degradation of SMX by NSOC activated PMS;
FIG. 16 degradation pathway of SMX.
Detailed Description
The technical scheme of the invention is further explained and illustrated in the following by the form of specific examples.
(1) Preparation of Co-MOF containing N, S element:
co (CH) 3 COO) 2 ·4H 2 O(0.54g,2.27mmol)、H 2 tdc (0.42 g,2.47 mmol), and 4,4' -bpy (0.444 g,2.84 mmol) were dissolved in 30mL of an aqueous solution. The resulting mixture was transferred to an autoclave and heated to 130℃for 6 hours, cooled to room temperature to give a pink crystal Co-MOF containing N, S elements.
(2) N, S doped Co/CoO/Co 9 S 8 Preparing an NSOC catalyst;
putting the Co-MOF containing N, S element prepared in the step (1) into a tube furnace, and adding N into the furnace 2 Flowing under air at 5 deg.C for min -1 Heating to 800 ℃ at the heating rate of (3) h, naturally cooling to room temperature to obtain N, S doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC catalyst
To verify Co/CoO/Co 9 S 8 The effect of @ NSOC on activating PMS was studied for its performance in degrading Sulfamethoxazole (SMX). Degradation experiments were performed in a 100mL beaker, which was placed in a thermostatic water bath at a reaction temperature of 25 ℃. 5mg Co/CoO/Co 9 S 8 NSOC was homogeneously dispersed in SMX (20 mg L -1 50 mL) of the solution, 12.3mg of PMS was added, and after mixing uniformly, l mL of the reaction solution was taken at a certain interval, the obtained sample was filtered through a 0.22 μm filter membrane, andimmediately quenched with 1mL of saturated sodium thiosulfate solution and the SMX content was determined by High Performance Liquid Chromatography (HPLC).
As shown in FIG. 1, successful Co-MOF preparation and Co/CoO/Co were confirmed by XRD 9 S 8 Constituent components of @ NSOC. The diffraction peak position accords with Co indicated by a standard card (JCPDS 15-0806), coO indicated by a standard card (JCPDS 43-1004) and Co indicated by a standard card (JCPDS 02-1459) 9 S 8 Wherein the diffraction peak at 44.2 ° coincides with the (1 1 1) crystal plane of Co, the diffraction peak at 42.4 ° coincides with the (2 0) crystal plane of CoO, and the diffraction peaks at 31.1 ° and 49.5 ° coincide with Co, respectively 9 S 8 The crystal faces (2 2 2) and (3 3 1) are consistent, and the composite material is proved to contain the components.
As shown in FIG. 2, co-MOF is a structure with smooth surface and stacked into blocks from sheets, and Co/CoO/Co obtained after calcination 9 S 8 The @ NSOC sheet structure is more obvious, a sheet stacking state is shown, the thickness of the nano sheet is about 300 a nm a, the surface is rough, small raised particles are fully distributed, the specific surface area of the catalyst can be increased, and the contact between pollutants and the catalyst is facilitated.
FIG. 3 shows Co/CoO/Co 9 S 8 TEM image of @ NSOC. It can be seen from fig. 3 (a) that the metal in the catalyst exists in the form of nano particles and is coated in a carbon layer, and the carbon layer coating structure can effectively reduce overflow of metal ions. From the HRTEM image, the lattice fringes of the various substances can be clearly seen, wherein lattice fringes with a spacing of 0.30nm and 0.28nm indicate the presence of Co 9 S 8 Corresponding to (3 3 1) and (2 2 2) crystal planes, respectively; lattice fringes with a spacing of 0.21nm correspond to the (2 0 0) crystal plane of CoO; the lattice fringes at a spacing of 0.20nm correspond to the (1 1) crystal plane of Co (FIG. 3 (b)), all consistent with XRD results. The above results indicate Co/CoO/Co 9 S 8 Successful preparation of the @ NSOC nanocomposite.
Co/CoO/Co as shown in FIG. 4 9 S 8 Fourier infrared spectrum (FT-IR) plot of @ NSOC. Wherein the characteristic peak is located at 620cm -1 The nearby absorption peak is generated by sulfonic acid group, 1118cm -1 The peak at this point is the tensile vibration peak of s=o, 1630cm -1 The nearby absorption peak is generated by-OH in-plane bending vibration [15] ,2924cm -1 The peak at which corresponds to-CH 2 Asymmetric stretching vibration peak, which is located at 3000-3600cm -1 The broad peak in the range is the tensile vibration peak of O-H. The above results all indicate Co/CoO/Co 9 S 8 The @ NSOC contains abundant hydrophilic functional groups, which is beneficial to dispersing in water.
As shown in FIG. 5, co/CoO/Co was studied by nitrogen adsorption experiments 9 S 8 Specific surface area and pore size of @ NSOC. The results show that Co/CoO/Co 9 S 8 Specific surface area of @ NSOC (209.0267 m 2 ·g -1 ) Specific Co-MOF (62.8792 m 2 ·g -1 ) The improvement is 3.3 times. This indicates that Co/CoO/Co obtained by calcination 9 S 8 The @ NSOC has a plurality of new pore channels and increased specific surface area.
Co/CoO/Co as in FIG. 6 9 S 8 The aqueous dispersion and magnetic properties of NSOC were tested and the catalyst was added to water to see its uniform dispersion in aqueous solution, which was shown to have typical ferromagnetism by the hysteresis loop. Studies have shown that when the saturation magnetization (Ms) of the magnetic material exceeds 16.3 emu.g -1 When the magnetic field is applied, the separation of the magnetic field from the solution can be realized. Tests show that Co/CoO/Co 9 S 8 Ms of @ NSOC catalyst was 22.71 emu. G -1 . And Ms of the catalyst obtained after one cycle can still reach 17.56 emu.g -1 . The result shows that the catalyst has typical weak ferromagnetism, is easy to separate from water body, and is favorable for recycling water.
As shown in FIG. 7, it was further found by contact angle testing that, due to Co/CoO/Co 9 S 8 The @ NSOC powder is extremely hydrophilic, and water drops can quickly permeate into the catalyst after contacting the catalyst, so that the hydrophilicity of the catalyst is greatly improved compared with Co-MOF.
As shown in FIG. 8, co/CoO/Co was studied by XPS 9 S 8 Surface composition and chemical state of @ NSOC. XPS photoelectron spectroscopy showed the presence of Co, C, N, S and O elements. High resolution at S2 pIn the map, the peak at 168.7eV may be a sulfonic acid group, which is a hydrophilic group effective to enhance the hydrophilicity of the catalyst. The characteristic peaks of N are attributed to pyridine-N, co-N, pyrrole-N and graphite-N. It is believed that all N bond configurations contribute to catalytic activity, except for oxides of nitrogen. In particular, graphite-N has been shown to provide more valence electrons to enhance conductivity and catalytic activity.
As shown in FIG. 9, the effect of the catalyst on activating PMS was investigated when Co/CoO/Co was added simultaneously 9 S 8 At the time of @ NSOC and PMS, 98.78% of SMX can be degraded within 10min, and the first-order reaction kinetic constant is as high as 1.31min -1 The above results all indicate that the prepared Co/CoO/Co 9 S 8 The @ NSOC had very good activation of PMS.
As shown in fig. 10, factors that may affect the degradation rate were explored. With respect to the catalyst and PMS amounts, the reaction rate does not change much as the amount increases to a certain level. For external factors, when the pH of the solution is neutral, the reaction rate is the fastest; the reaction progress is accelerated when the temperature increases.
As shown in fig. 11, since carbonate, chloride ion, phosphate and humic acid are commonly present in the water body, their effect on SMX degradation was studied. The result shows that the catalyst has certain ion interference resistance.
As shown in FIG. 12, the performance of the catalyst for degrading SMX in real water body is studied, when tap water is used as a solvent, although the SMX removal rate can reach about 98% in 10min, the degradation rate is obviously reduced compared with that of a control group, and when the actual river water is used as the solvent, the SMX removal rate is reduced to 87.30% in 10 min. This suggests that some components in real bodies of water may have an inhibitory effect on the degradation of SMX, but this inhibitory effect is not strong.
As shown in FIG. 13, co/CoO/Co 9 S 8 After five continuous cyclic degradation SMX experiments, the degradation rate of SMX is not obviously reduced, which indicates Co/CoO/Co 9 S 8 The @ NSOC has higher recycling property.
FIG. 14 is Co/CoO/Co 9 S 8 Before SMX is circularly degraded by @ NSOCThe XRD pattern is degraded in five times of continuous cycles, co/CoO/Co 9 S 8 The composition of @ NSOC did not change significantly, further demonstrating Co/CoO/Co 9 S 8 The @ NSOC catalyst has better cycle stability.
As shown in FIG. 15, the results of the radical trapping experiments indicate that Co/CoO/Co is comparable to the quencher-free system 9 S 8 The @ NSOC activated PMS degradation SMX reaction was inhibited by the quenchers furfuryl alcohol (FFA), p-Benzoquinone (BQ), methanol (ME) and t-butanol (TBA).
As shown in fig. 16, LC-MS experiments were performed in order to propose a degradation pathway. The degradation route is mainly divided into that methyl on the isoxazole ring is oxidized into carboxyl; the oxidation of isoxazole rings, which breaks due to the attack of active oxygen on the bond between sulphur and nitrogen, is a small molecule compound whose chemical bond is broken through a series of breaks and eventually forms.
Claims (10)
1. N, S Co-doped Co/CoO/Co 9 S 8 The preparation method of the @ NSOC catalyst is characterized by comprising the following steps:
(1) Preparation of Co-MOF containing N, S element:
2.2 to 2.3mmol Co (CH) 3 COO) 2 ·4H 2 O, 2.4-2.5 mmol of 2, 5-thiophene dicarboxylic acid, and 2.8-2.9 mmol of 4,4' -bipyridine are dissolved in 30mL of water; transferring the obtained mixture into a high-pressure reaction kettle, heating for 5-7 hours at 128-132 ℃, and cooling to room temperature to obtain pink crystal Co-MOF;
(2) N, S doped Co/CoO/Co 9 S 8 Preparation of @ NSOC catalyst:
putting the Co-MOF containing N, S element prepared in the step (1) into a tube furnace, and under a protective atmosphere, keeping the temperature at 4-6 ℃ for min -1 Heating to 790-810 deg.C, maintaining for 2.5 hr or more, naturally cooling to room temperature to obtain Co/CoO/Co 9 S 8 @ NSOC catalyst.
2. The method according to claim 1, wherein Co (CH 3 COO) 2 ·4H 2 2.27mmol of O, 2.47mmol of 2, 5-thiophenedicarboxylic acid and 2.84mmol of 4,4' -bipyridine.
3. The process according to claim 1, wherein the heating temperature in step (1) is 130 ℃.
4. The method according to claim 1, wherein the heating time in step (1) is 6 hours.
5. The method according to claim 1, wherein the temperature rise rate in step (2) is 5℃min -1 。
6. The process according to claim 1, wherein the holding temperature in the tube furnace in step (2) is 800 ℃.
7. The process according to claim 1, wherein the holding time in the tube furnace in step (2) is 3 hours.
8. N, S Co/CoO/Co Co-doped by the method according to any one of claims 1 to 7 9 S 8 @ NSOC catalyst.
9. A Co/CoO/Co Co-doped according to claim 8 at N, S 9 S 8 Use of an NSOC catalyst for degrading SMX.
10. The use according to claim 9, characterized in that it comprises in particular the following steps: the catalyst and the peroxymonosulfate were added to an aqueous solution containing SMX at a catalyst concentration of 100mg/L and a peroxymonosulfate concentration of 0.8mM.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210357568.3A CN114713260B (en) | 2022-04-04 | 2022-04-04 | N, S Co-doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC, preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210357568.3A CN114713260B (en) | 2022-04-04 | 2022-04-04 | N, S Co-doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC, preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114713260A CN114713260A (en) | 2022-07-08 |
CN114713260B true CN114713260B (en) | 2023-06-16 |
Family
ID=82241504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210357568.3A Active CN114713260B (en) | 2022-04-04 | 2022-04-04 | N, S Co-doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC, preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114713260B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105731609A (en) * | 2014-12-10 | 2016-07-06 | 吉林师范大学 | Porous carbon electrode based on metal organic framework material, and preparation method thereof |
CN109650484A (en) * | 2019-01-22 | 2019-04-19 | 南通大学 | A kind of waste water treating agent and preparation method thereof |
CN110339852A (en) * | 2019-07-15 | 2019-10-18 | 商丘师范学院 | A kind of CoO@nitrogen sulphur codope carbon material/CdS composite photocatalyst material, preparation method and applications |
CN112246270A (en) * | 2020-10-20 | 2021-01-22 | 青岛理工大学 | N/P co-doped MOFs-C-based material and preparation method and application thereof |
CN113559912A (en) * | 2021-08-16 | 2021-10-29 | 哈尔滨工业大学(深圳) | Nitrogen-sulfur co-doped graphene supported cobalt catalyst, and preparation method and application thereof |
-
2022
- 2022-04-04 CN CN202210357568.3A patent/CN114713260B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105731609A (en) * | 2014-12-10 | 2016-07-06 | 吉林师范大学 | Porous carbon electrode based on metal organic framework material, and preparation method thereof |
CN109650484A (en) * | 2019-01-22 | 2019-04-19 | 南通大学 | A kind of waste water treating agent and preparation method thereof |
CN110339852A (en) * | 2019-07-15 | 2019-10-18 | 商丘师范学院 | A kind of CoO@nitrogen sulphur codope carbon material/CdS composite photocatalyst material, preparation method and applications |
CN112246270A (en) * | 2020-10-20 | 2021-01-22 | 青岛理工大学 | N/P co-doped MOFs-C-based material and preparation method and application thereof |
CN113559912A (en) * | 2021-08-16 | 2021-10-29 | 哈尔滨工业大学(深圳) | Nitrogen-sulfur co-doped graphene supported cobalt catalyst, and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114713260A (en) | 2022-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Oxygen vacancies-enriched Cu/Co bimetallic oxides catalysts for high-efficiency peroxymonosulfate activation to degrade TC: Insight into the increase of Cu+ triggered by Co doping | |
Chen et al. | Synergy effect between adsorption and heterogeneous photo-Fenton-like catalysis on LaFeO3/lignin-biochar composites for high efficiency degradation of ofloxacin under visible light | |
Xie et al. | Porous NiFe-oxide nanocubes derived from prussian blue analogue as efficient adsorbents for the removal of toxic metal ions and organic dyes | |
CN109529793B (en) | Preparation method and application of magnetic hydrotalcite loaded titanium dioxide composite material | |
Gao et al. | Visible light induced photocatalytic reduction of Cr (VI) by self-assembled and amorphous Fe-2MI | |
Li et al. | Adsorption and photocatalytic desorption toward Cr (VI) over defect-induced hierarchically porous UiO-66-(OH) 2: a sustainable approach | |
Jiang et al. | Superhydrophilic N, S, O-doped Co/CoO/Co9S8@ carbon derived from metal-organic framework for activating peroxymonosulfate to degrade sulfamethoxazole: performance, mechanism insight and large-scale application | |
Zhang et al. | Metal–organic frameworks and their composites for environmental applications | |
Wang et al. | Adsorptive catalysis of hierarchical porous heteroatom-doped biomass: from recovered heavy metal to efficient pollutant decontamination | |
CN114425340B (en) | Preparation of biochar modified cobalt-iron bimetallic composite catalyst and application of biochar modified cobalt-iron bimetallic composite catalyst in catalytic degradation of tetracycline | |
Wu et al. | Adsorption mechanism and kinetics of azo dye chemicals on oxide nanotubes: A case study using porous CeO 2 nanotubes | |
Zhu et al. | Nano-manganese oxides-modified biochar for efficient chelated copper citrate removal from water by oxidation-assisted adsorption process | |
Zhang et al. | Effect of Bi5O7I/calcined ZnAlBi-LDHs composites on Cr (VI) removal via adsorption and photocatalytic reduction | |
CN113351212B (en) | Nickel-doped hydrotalcite-like compound with rich oxygen vacancies and preparation method and application thereof | |
Du et al. | Coupling ultrafine plasmonic Co3O4 with thin-layer carbon over SiO2 nanosphere for dual-functional PMS activation and solar interfacial water evaporation | |
CN107335422B (en) | Preparation method of carbon functionalized cerium oxide | |
Sun et al. | Magnetic Fe 3 O 4@ CoFe-LDH nanocomposite heterogeneously activated peroxymonosulfate for degradation of azo-dye AO7 | |
Zhang et al. | Bismuth (III)-based metal-organic framework for tetracycline removal via adsorption and visible light catalysis processes | |
Li et al. | Well-defined bimetal oxides derived from Prussian blue analogues with regulable active sites for phosphate removal | |
Zhang et al. | Bimetal-organic framework MIL-53 (Fe, Ni) stimulates peroxydisulfate to degrade rhodamine B: Properties and degradation mechanism | |
Zhu et al. | Constructing a multivalent Co-confined N-doped C–Si hybrid hollow nanoreactor for synchronous pollutant mineralization and solar-driven interfacial water regeneration | |
CN113189268A (en) | Method for degrading organic pollutants by catalytic ozone | |
CN114713260B (en) | N, S Co-doped Co/CoO/Co 9 S 8 Nano catalyst @ NSOC, preparation method and application thereof | |
CN116943692A (en) | Bismuth ferrite/bismuth oxysulfate/ferric oxide strip composite material and preparation method and application thereof | |
CN114984980B (en) | Dual-function FeCo 2 O 4 CdS tubular micromotor, and preparation method and application thereof |
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 |