CN115555025A - Preparation method of high-dispersion cobalt-molybdenum bimetallic catalyst - Google Patents
Preparation method of high-dispersion cobalt-molybdenum bimetallic catalyst Download PDFInfo
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- CN115555025A CN115555025A CN202211365973.6A CN202211365973A CN115555025A CN 115555025 A CN115555025 A CN 115555025A CN 202211365973 A CN202211365973 A CN 202211365973A CN 115555025 A CN115555025 A CN 115555025A
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- molybdenum
- bimetallic catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000006185 dispersion Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims description 40
- 239000000523 sample Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012520 frozen sample Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 230000033558 biomineral tissue development Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- MDKXFHZSHLHFLN-UHFFFAOYSA-N alumanylidynecobalt Chemical compound [Al].[Co] MDKXFHZSHLHFLN-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000405 induce cancer Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- C02F2101/38—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
Abstract
A preparation method of a high-dispersion cobalt-molybdenum bimetallic catalyst belongs to the technical field of new materials and environmental purification, and particularly relates to a high-dispersion Co 2 Mo 3 O 8 A catalyst and a method for treating organic wastewater by using the catalyst to activate persulfate. The method effectively solves a series of practical problems of low reaction mass transfer efficiency and low mineralization rate of the bimetallic catalyst at the present stage; the cobalt-molybdenum bimetallic catalyst prepared by the method has excellent catalytic performance and can meet the requirements of practical application. The method specifically comprises the following steps: step 1, weighing urea, soluble salt of cobalt and soluble salt of molybdenum, dissolving in 100ml of distilled water, and stirring uniformly to obtain a solution A; and 2, transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours.
Description
Technical Field
The inventionBelongs to the technical field of new materials and environmental purification, and particularly relates to high-dispersion Co 2 Mo 3 O 8 A catalyst and a method for treating organic wastewater by using the catalyst to activate persulfate.
Background
With the rapid development of socioeconomic and the intensive development of chemical, pharmaceutical and agricultural industries, many compounds, such as pesticides, antibiotics and dyes, are introduced into the aquatic environment. They can be accumulated in the human body by biological amplification, destroy the endocrine system, reproductive system and immune system of the human body, induce cancer and nervous system diseases, and have a "triple effect". Further poses great threat to human health and also has serious influence on the sustainable development and the rapid and green increase of economy of the society. Among them, the toxic, harmful and difficult-to-degrade organic pollutants are the key and difficult points in the process of treating water environmental pollution. Therefore, it is crucial to find a new, efficient and environmentally friendly technology for degrading high concentration organic pollutants. Based on sulfate radicals (SO) 4 · - ) The advanced oxidation technology is a novel water treatment technology developed in recent years, and has attracted attention due to the advantages of high-efficiency treatment of refractory organic matters, small environmental pollution and the like. Sulfate radical (SO) 4 · - ) Has higher oxidation-reduction potential (SO) than hydroxyl radical 4 · - ：E 0 ＝2.5-3.1V，·OH：E 0 = 1.8-2.7V), and a longer half-life (T · SO) 4 · - =4 × 10-5s, t · OH =10-9 s), and the hydroxyl radical oxidizes organic molecules mainly by abstraction or addition reaction of hydrogen atoms, while the sulfate radical is more prone to directly perform electron transfer reaction, thus greatly increasing the contact chance between the radical and pollutants, facilitating degradation and mineralization of pollutants, and having great prospects in the field of environmental pollution control.
The existing research shows that the transition metal ions can effectively activate persulfate to generate a large number of free radicals, wherein cobalt ions (Co) are used 2+ ) The catalytic activity of (2) is highest. However, the metal ions generally have certain toxicity, so that the process is greatly limited in water treatment applicationMeanwhile, metal ions in a homogeneous reaction system are difficult to recover, so that unnecessary consumption of the catalyst is caused, and the process operation cost is increased. The problem can be effectively solved by using heterogeneous cobalt-based catalyst to activate persulfate, therefore, researchers developed a large amount of solid-phase cobalt-based catalytic materials, co 3 O 4 Shows stronger catalytic performance when activating persulfate, but Co exists in the single-metal catalyst 2+ /Co 3+ The rate-limiting reaction is greatly influenced by the pH value of the wastewater, and the secondary pollution to the environment can be caused due to serious leaching of metal ions. Therefore, improving the comprehensive performance of the cobalt-based catalyst is always important in the research of the field of catalytic materials.
Currently, in the modification of cobalt-based catalysts: the more common method is to introduce other transition metal elements to prepare the bimetallic catalyst. The bimetallic catalyst can effectively improve the catalytic activity of the single metal catalyst, so that each metal can exert the chemical property thereof, and the bimetallic catalyst has very wide potential. Although the existing cobalt-based bimetallic catalysts such as aluminum-cobalt layered double hydroxide and cobalt-manganese spinel type oxide reduce the leaching of metal ions, the existing cobalt-based bimetallic catalysts have the defects of low mass transfer efficiency, low mineralization rate and the like of reaction to a certain extent, so that various limitations caused by heterogeneous catalysis still cannot be effectively broken through.
In summary, the following steps: the cobalt-based bimetallic catalyst prepared by the method is environment-friendly, has excellent catalytic performance, realizes higher mineralization rate and lower leaching rate, and meets the requirements of practical application.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a high-dispersion cobalt-molybdenum bimetallic catalyst. The method effectively solves a series of practical problems of low reaction mass transfer efficiency and low mineralization rate of the bimetallic catalyst at the present stage; the cobalt-molybdenum bimetallic catalyst prepared by the method has excellent catalytic performance and can meet the requirements of practical application.
In order to achieve the purpose, the preparation method of the high-dispersion cobalt-molybdenum bimetallic catalyst specifically comprises the following steps:
and 3, centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by using deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃.
And 5, freezing the calcined sample in liquid nitrogen for 20-60min.
The high-dispersion cobalt-molybdenum bimetallic catalyst can be used for catalytic oxidation degradation of organic pollutants.
The soluble salt of cobalt is cobalt chloride hexahydrate soluble salt; the soluble salt of molybdenum is ammonium heptamolybdate tetrahydrate soluble salt.
The mol ratio of the urea to the soluble salt of the cobalt to the soluble salt of the molybdenum is 3: 1.
The hydrogen atmosphere is a hydrogen-nitrogen mixed gas with the hydrogen content of 5%.
The calcination temperature is 600 to 800 ℃, and more preferably 700 ℃.
The invention has remarkable effect.
The high-dispersion cobalt-molybdenum bimetallic catalyst has high catalytic performance, and the removal efficiency of 30mg/L rhodamine B dye in 10 minutes under a neutral condition reaches 99.9 percent (as shown in figure 7).
Compared with the prior art, the invention has the following advantages: 1. by introducing molybdenum in a lower valence state and simultaneously presenting Co (II) and Co (III) on the surface of the catalyst (as shown in figure 4), the two can realize rapid reaction with the assistance of the molybdenum in a lower valence state (as shown in figure 5)The persulfate is activated to continuously generate SO 4 · - .2. During the preparation of the catalyst, oxygen vacancy is introduced (as shown in figure 6), a large amount of singlet oxygen is generated in the whole system, and both free radicals and non-free radicals participate in the degradation of organic matters. 3. The catalyst is in a high-dispersion state by adopting low-temperature freezing treatment, and more active sites are exposed, so that the excellent degradation performance of the catalyst is ensured. 4. The prepared cobalt-molybdenum bimetallic catalyst has high purity, no obvious impurity and purity up to more than 98%.
Drawings
Figure 1 XRD scanning test patterns of samples of example 1 and example 3.
FIG. 2 is a scanning electron micrograph of a sample under different preparation conditions.
FIG. 3 specific surface area test charts of the samples of example 1 and example 3.
FIG. 4 XPS plot of Co element of sample of comparative example 3
FIG. 5 XPS plot of Mo element for sample of comparative example 3
FIG. 6 XPS plot of the O element of the sample of comparative example 3
FIG. 7 is a graph showing degradation of rhodamine B dye by the sample in the example.
FIG. 8 is a degradation diagram of rhodamine B dye for samples in the example and the comparative example.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1.
A high-dispersity Co-Mo bimetal catalyst with the chemical formula of Co 2 Mo 3 O 8 . The preparation method comprises the following steps: 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate are weighed, dissolved in 100ml of distilled water, and the solution A is obtained after uniform stirring. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. Centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. The dried purple powder is put into a tube furnace, and then is heated to 700 ℃ in the hydrogen atmosphere for calcination at a fixed heating rateSet at 5 deg.C/min. The samples were stored at 600-800 ℃ for 1h. The cobalt-molybdenum bimetallic catalyst of the invention is obtained and is marked as CMO-0.
Powder samples were tested using a DX 2500X-ray diffractometer with a 2 theta range of 10-90 DEG, and XRD test results are shown in figure 1. As can be seen from FIG. 1, the sample is mixed with Co 2 Mo 3 O 8 The standard PDF card basically and completely conforms to the standard PDF card, which shows that the method can prepare purer Co 2 Mo 3 O 8 And (3) nano powder. The scanning electron micrograph of the catalyst CMO-0 of this example is shown in the left image of FIG. 2, and it can be seen that a small amount of agglomeration occurred in the sample.
Example 2.
A high-dispersity Co-Mo bimetal catalyst with Co as chemical formula 2 Mo 3 O 8 . The preparation method comprises the following steps: 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate are weighed, dissolved in 100ml of distilled water, and the solution A is obtained after uniform stirring. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. Centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. And (3) putting the dried purple powder into a tubular furnace, and then heating to 700 ℃ in a hydrogen atmosphere for calcining, wherein the heating rate is fixed at 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. And (3) freezing the calcined sample in liquid nitrogen for 20min, and then putting the sample into a planetary ball mill for ball milling for 1h. The high-dispersion cobalt-molybdenum bimetallic catalyst is obtained and is marked as CMO-1.
The scanning electron microscope picture of the CMO-1 catalyst is shown in the right picture of FIG. 2; as can be seen from the figure, co prepared after low temperature freezing 2 Mo 3 O 8 The powder particles are refined, and compared with the sample in the embodiment 1, the sample has the advantages of obviously reduced particle size and higher dispersion degree.
Example 3
A high-dispersity Co-Mo bimetal catalyst with Co as chemical formula 2 Mo 3 O 8 . The preparation method comprises the following steps: 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of tetrahydrate are weighedDissolving ammonium heptamolybdate in 100ml of distilled water, and uniformly stirring to obtain a solution A. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. And centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by using deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. And (3) putting the dried purple powder into a tube furnace, heating to 700 ℃ in a hydrogen atmosphere, and calcining at a fixed heating rate of 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. And (3) freezing the calcined sample in liquid nitrogen for 40min, and then putting the sample into a planetary ball mill for ball milling for 1h. The high-dispersion cobalt-molybdenum bimetallic catalyst is obtained and is marked as CMO-2.
The specific surface area test result of the CMO-2 material is shown in FIG. 3, and the specific surface area of the sample of example 1 is 17.334m 2 ·g -1 Example 3 has a specific surface area of 36.413m 2 ·g -1 . This shows that the specific surface area of the CMO-2 material is greatly improved, which is beneficial to increasing the catalytic activity.
XPS spectra of Co, mo and O elements for CMO-2 samples are shown in FIGS. 4, 5, 6. FIG. 4 shows that the Co element includes Co 2+ And Co 3+ . FIG. 5 shows that the lower Mo content in CMO-2 is higher than in the sample of example 1. Figure 6 shows that O vacancies are present at the catalyst surface. These factors have a significant effect on catalytic performance.
The high-dispersion cobalt-molybdenum bimetallic catalyst prepared by the embodiment is used for activating persulfate to test the degradation performance of the persulfate to rhodamine B, and the detailed experimental conditions are as follows: placing 10mg of CMO-2 catalyst into 100mL of rhodamine B solution, wherein the concentration of rhodamine B is 30mg/L, the experimental temperature is 26 ℃, adjusting the pH value of the solution to 7, and ensuring uniform mixing through a magnetic stirrer. After adsorption is saturated in 30min, 10mg of persulfate is added to promote degradation reaction, the degradation effect graph of rhodamine B is shown in figure 7, the degradation efficiency of rhodamine B reaches 99.9% in 10min, and the high-efficiency characteristic of the catalyst is verified.
Example 4
A high-dispersity Co-Mo bimetal catalyst with Co as chemical formula 2 Mo 3 O 8 . The preparation method comprises the following steps: 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate are weighed, dissolved in 100ml of distilled water, and the solution A is obtained after uniform stirring. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. Centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. And (3) putting the dried purple powder into a tubular furnace, and then heating to 700 ℃ in a hydrogen atmosphere for calcining, wherein the heating rate is fixed at 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. And (3) freezing the calcined sample in liquid nitrogen for 60min, and then putting the sample into a planetary ball mill for ball milling for 1h. The high-dispersion cobalt-molybdenum bimetallic catalyst is obtained and is marked as CMO-3.
This sample differs from examples 2 and 3 in that the sample was calcined and then frozen for a longer period of time. Under the same experimental conditions, the catalytic degradation rate is reduced.
Comparative example 1.
A high-dispersity Co-Mo bimetal catalyst with Co as chemical formula 2 Mo 3 O 8 . The preparation method comprises the following steps: 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate are weighed, dissolved in 100ml of distilled water, and the solution A is obtained after uniform stirring. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. Centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. And (3) putting the dried purple powder into a tubular furnace, and then heating to 700 ℃ in a hydrogen atmosphere for calcining, wherein the heating rate is fixed at 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. And (3) freezing the calcined sample in liquid nitrogen for 60min, and then putting the sample into a planetary ball mill for ball milling for 1h. The high-dispersion cobalt-molybdenum bimetallic catalyst is obtained.
Cobalt molybdenum bimetallic catalyst prepared in air atmosphere and having chemical formula of CoMoO 4 . Weighing 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate, dissolving in 100ml of distilled water, and stirring uniformlyTo obtain solution A. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. Centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. And (3) putting the dried purple powder into a tubular furnace, and then heating to 700 ℃ in an air atmosphere for calcining, wherein the heating rate is fixed at 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. Obtaining a cobalt molybdenum bimetallic catalyst, noted as O 2 -CMO. The samples prepared by calcining in the air atmosphere as described above were subjected to the catalytic performance test under the same experimental conditions as in example 3, and the results are shown in fig. 8.
Comparative example 2.
A high-dispersity Co-Mo bimetal catalyst with Co as chemical formula 2 Mo 3 O 8 . The preparation method comprises the following steps: 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate are weighed, dissolved in 100ml of distilled water, and the solution A is obtained after uniform stirring. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. Centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. And (3) putting the dried purple powder into a tubular furnace, and then heating to 700 ℃ in a hydrogen atmosphere for calcining, wherein the heating rate is fixed at 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. And (3) freezing the calcined sample in liquid nitrogen for 60min, and then putting the sample into a planetary ball mill for ball milling for 1h. The high-dispersion cobalt-molybdenum bimetallic catalyst is obtained.
Cobalt molybdenum bimetallic catalyst prepared in nitrogen atmosphere, chemical formula CoMoO 4-x . 3mmol of urea, 1mmol of cobalt chloride hexahydrate and 1mmol of ammonium heptamolybdate tetrahydrate are weighed, dissolved in 100ml of distilled water, and the solution A is obtained after uniform stirring. Transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours. And centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by using deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃. The dried purple powder is put into a tube furnace and then put into nitrogen atmosphereHeating to 700 ℃ for calcination, and fixing the heating rate at 5 ℃/min. The samples were stored at 600-800 ℃ for 1h. Obtaining the cobalt-molybdenum bimetallic catalyst, marked as N 2 -CMO. The sample prepared by calcining in a nitrogen atmosphere as described above was subjected to the catalytic performance test under the same experimental conditions as in example 3, and the results are shown in fig. 8.
The comparative experimental results shown in fig. 8 show that the catalytic performance of the samples prepared by calcination in air and nitrogen, respectively, is much lower than that of the present invention. The reason for this is that the catalyst prepared by calcination in air is agglomerated and more active sites are not exposed. The sample prepared by calcining in the nitrogen atmosphere has less introduced oxygen vacancy, and the whole reaction mainly comprises SO4 DEG - Is led.
Claims (5)
1. A preparation method of a high-dispersion cobalt-molybdenum bimetallic catalyst is characterized by comprising the following steps:
step 1, weighing urea, soluble salt of cobalt and soluble salt of molybdenum, dissolving in 100ml of distilled water, and stirring uniformly to obtain a solution A;
step 2, transferring the solution A into a polytetrafluoroethylene hydrothermal reaction kettle, heating to 120 ℃, and keeping for 10 hours;
step 3, centrifuging the precipitate obtained by the reaction, washing the precipitate for 1 to 3 times by using deionized water, putting the washed precipitate into a drying oven, and drying the precipitate for 10 to 15 hours at the temperature of between 60 and 90 ℃;
step 4, placing the dried purple powder into a tube furnace, and then heating and calcining in a hydrogen atmosphere at a fixed heating rate of 5 ℃/min; storing the sample at 600-800 deg.C for 1h;
step 5, freezing the calcined sample in liquid nitrogen for 20-60min;
step 6, putting the frozen sample into a planetary ball mill, and performing ball milling for 1 hour; the high-dispersion cobalt-molybdenum bimetallic catalyst is obtained.
2. The method for preparing a highly dispersed cobalt molybdenum bimetallic catalyst as in claim 1, wherein the soluble salt of cobalt is a soluble salt of cobalt chloride hexahydrate; the soluble salt of molybdenum is ammonium heptamolybdate tetrahydrate soluble salt.
3. The preparation method of the highly dispersed cobalt molybdenum bimetallic catalyst according to claim 1, characterized in that the molar ratio of the urea to the soluble salt of cobalt to the soluble salt of molybdenum is 3.
4. The method for preparing a highly dispersed cobalt molybdenum bimetallic catalyst as in claim 1, wherein the hydrogen atmosphere is a mixed gas of hydrogen and nitrogen with a hydrogen content of 5%.
5. The method for preparing a highly dispersed cobalt molybdenum bimetallic catalyst as in claim 1, wherein the calcination temperature is 600-800 ℃.
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