CN114433091B - Cu-Co bimetallic spinel type catalyst and preparation thereof and application thereof in methane production by reduction and dechlorination of methylene dichloride - Google Patents
Cu-Co bimetallic spinel type catalyst and preparation thereof and application thereof in methane production by reduction and dechlorination of methylene dichloride Download PDFInfo
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- CN114433091B CN114433091B CN202210090440.5A CN202210090440A CN114433091B CN 114433091 B CN114433091 B CN 114433091B CN 202210090440 A CN202210090440 A CN 202210090440A CN 114433091 B CN114433091 B CN 114433091B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 25
- 239000011029 spinel Substances 0.000 title claims abstract description 25
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910017816 Cu—Co Inorganic materials 0.000 title abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 3
- 229910016507 CuCo Inorganic materials 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- -1 tetrabutylammonium tetrafluoroborate Chemical compound 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/50—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
- C25B11/0771—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide of the spinel type
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Abstract
The invention discloses a Cu-Co bimetallic spinel type catalyst, a preparation method thereof and application thereof in methane production by reduction and dechlorination of methylene dichloride. CuCo 2 O 4 The bimetallic spinel is a rod-shaped nano structure with protrusions on the surface, and the preparation method of the catalyst comprises the following steps: (1) Nitrate, urea and NH 4 F, dissolving in deionized water, and carrying out hydrothermal reaction for 6 hours at 150 ℃ to obtain a Cu-Co spinel precursor; (2) Calcining for 3 hours in a muffle furnace at 350 ℃ under the condition of different heating rates, and directly obtaining the catalyst. The catalyst is subjected to the electro-catalytic reduction of dichloromethane to perform dechlorination and methane production reaction at normal temperature and normal pressure, so that the high-efficiency dichloromethane reduction and dechlorination and methane production can be realized, and the catalyst has higher environmental and energy significance. In addition, the methane preparation method has simple operation and can realize safe and convenient preparation of pure gas-phase methane.
Description
Technical Field
The invention belongs to the field of catalytic reduction dechlorination, and particularly relates to preparation of a Cu-Co bimetallic spinel type catalyst and application of the catalyst in methane production through reduction dechlorination of methylene dichloride.
Background
Methane is an important fuel, and is the main component of natural gas, accounting for about 87% of natural gas. It can be used not only as fuel but also as a carbon source for vapor phase chemical deposition of amorphous silicon films for solar cells, methane as a raw material for pharmaceutical chemical synthesis, etc. At present, the synthesis of methane at home and abroad mainly adopts a high-temperature methanation technology. However, a great amount of heat is released in the methanation reaction process, so that the catalyst is easy to generate hot spots due to local overheating, the catalyst is sintered, and the catalytic activity and stability are reduced. Therefore, how to ensure the activity and stability of the catalyst is the key to solve the problem.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing the bimetallic spinel catalyst by a hydrothermal method, which can effectively remove C1 groups in methylene dichloride to obtain methane with high recovery added value, green and economic performance, and has the advantages of mild condition, strong operability and good application prospect.
The invention aims to provide a preparation method of a bimetallic spinel catalyst and the bimetallic spinel catalyst is used in the electro-reduction dechlorination process of methylene dichloride, and in order to achieve the purposes, the preparation method adopts the following technical scheme:
in one aspect, the present invention provides a spinel catalyst, the catalyst being CuCo 2 O 4 Bimetallic spinel, cuCo 2 O 4 The bimetallic spinel is a rod-shaped nano structure with protrusions on the surface.
Based on the scheme, further, the diameter of the rod-shaped nano structure is 200-300 nm, and more preferably 230nm; the specific surface area of the catalyst is 30-100 m 2 Preferably 61.03m 2 /g。
On the other hand, the invention provides a preparation method of the catalyst, wherein the catalyst is prepared by adopting a hydrothermal method, and the hydrothermal method comprises the following steps:
1) Copper salt, cobalt salt, urea and NH 4 F are sequentially dissolved in deionized water to obtain a solution A, wherein copper salt, cobalt salt, urea and NH in the solution A 4 The molar ratio of F is 1:2:10:6, more preferably 0.6M, 1.2M, 6M and 3.6M;
2) Uniformly stirring the solution A, and performing hydrothermal reaction at 140-170 ℃ for 6-24 h, and further preferably at 150 ℃ for 6h to obtain a solution B;
3) Alternately cleaning the solution B with deionized water and ethanol, centrifuging and drying to obtain a solid I;
4) Calcining the solid I in air at 350-450 ℃ for 3-12 h h, and more preferably at 350 ℃ for 3h to obtain the catalyst.
Based on the above scheme, further, in step 1), the copper salt and cobalt salt are Cu (NO 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 The volume of the solution A is 50 to 100mL, more preferably 72mL.
Based on the scheme, in the step 2), the stirring time is 30-60 min, more preferably 30min, and the volume of the reaction kettle is 100mL.
Based on the above scheme, in step 3), the total cleaning times are 6-10 times, more preferably 6 times, the drying temperature is 60-80 ℃ and the drying time is 12-24 hours.
Based on the above scheme, in step 4), the temperature rising rate during calcination is 1-5 ℃/min, and more preferably 2 ℃/min.
In yet another aspect, the present invention uses the bimetallic spinel catalyst prepared above for the electro-reductive dechlorination of methylene chloride.
Further, the reaction is carried out in a three-electrode single-chamber electrolytic cell reactor system; the bimetallic spinel catalyst is loaded on a working electrode of the electrolytic cell; the loading capacity of the metal spinel catalyst is 0.5-2.0 mg/cm 2 Further preferably 1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The working electrode is a carbon cloth electrode.
Further, the anode of the three-electrode single-chamber electrolytic cell is a Pt sheet electrode, and the reference electrode is Ag/AgCl/Me 4 NCl, the electrode solution is N, N-Dimethylformamide (DMF) and acetonitrile, and the DMF and CH 3 The volume ratio of CN is 3:1, more preferably 9mL and 3mL.
Further, the electrolyte of the electrolytic cell system is DMF solution; the concentration of the electrolyte tetrabutylammonium tetrafluoroborate is 0.1 to 0.5mol/L, and more preferably 0.1mol/L; the addition amount of the electrolyte is 50-100 mL, more preferably 50mL; the concentration of dichloromethane in the electrolyte is 0.01-0.1 mol/L; the constant potential is-2.14V to-2.94 VV (vs SCE).
Advantageous effects
1. The Cu-Co bimetallic spinel catalyst provided by the invention has excellent performance; cuCo with rod-like structure 2 O 4 Has larger surface area and higher porosity, is beneficial to the diffusion of electrolyte ions, provides enough active sites and provides a plurality of channels for the effective transmission of electrons/ions. Meanwhile, the Cu-Co bimetallic has good conductivity, and the electron transfer rate of a reaction system is accelerated.
2. Under the operating conditions provided by the invention, the Cu-Co bimetallic spinel catalyst with the rod-shaped structure has excellent catalytic performance in the electrocatalytic reduction of dichloromethane to methane, and is specifically characterized by the following points:
(1) High reactivity (148.83 umol) and methane selectivity (91.44%) superior to the platy Cu-Co bimetallic spinel catalyst;
(2) The stability is strong, the reaction is carried out for 40 hours, or the reaction is repeated for 6 times, and the activity is hardly reduced.
(3) The method has the advantages of simple process operation, mild conditions, high efficiency and no need of complex equipment, and is a methane production process with higher practical development potential.
Drawings
FIG. 1 is a scanning electron microscope image of catalyst 1;
FIG. 2 is a transmission electron microscope image of catalyst 1;
FIG. 3 is an X-ray diffraction pattern of catalyst 1;
FIG. 4 is a scanning electron microscope image of catalyst 6;
FIG. 5 is a scanning electron microscope image of catalyst 7;
fig. 6 is a scanning electron microscope image of the catalyst 8.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Preparation of a bimetallic spinel catalyst:
(1) 0.145g Cu (NO) 3 ) 2 ·3H 2 O、0.349g Co(NO 3 ) 2 ·6H 2 O, 0.360g of urea and 0.1333g of NH 4 F is dissolved in 72mL of deionized water, and solution A is obtained after complete dissolution.
(2) Placing the solution A on a magnetic stirrer, stirring for 30min, transferring to a 100mL high-temperature reaction kettle, and screwing;
(3) Placing the screwed high-temperature reaction kettle in an oven, and carrying out hydrothermal reaction for 6 hours at 150 ℃ to obtain a reacted solution B;
(4) Alternately cleaning the solution B with deionized water and ethanol for 6 times, and centrifuging at a centrifugal speed of 8000r/min for 5min to obtain a solid I;
(5) The solid I was dried in an oven at 70℃for 24h and the dried solid I was transferred to a crucible.
(6) Calcining the crucible in muffle furnace at 350deg.C for 3 hr at heating rate of 2deg.C/min, naturally cooling to room temperature to obtain copper cobaltate (CuCo) 2 O 4 ) The bimetallic spinel catalyst is named as catalyst 1;
from the scanning electron microscope images, transmission electron microscope images and X-ray diffraction patterns of FIGS. 1, 2 and 3, it was found that the catalyst 1 was copper cobaltate (CuCo) having a rod-like nanostructure with good crystallinity 2 O 4 ) Bimetallic spinels.
(7) The catalyst is subjected to the dechlorination reaction of the electrocatalytic reduction dichloromethane under normal temperature and normal pressure, and is carried out in a three-electrode single-chamber electrolytic cell reactor system, wherein the anode is a Pt sheet electrode, and the reference electrode is Ag/AgCl/Me 4 NCl in DMF+CH 3 CN (volume ratio of 3:1) The working electrode is copper cobaltate (CuCo 2 O 4 ) The loading of the bimetallic spinel catalyst is 1.0mg/cm 2 50mL of 0.1mol/L DMF solution of tetrabutylammonium tetrafluoroborate, 0.1mol/L dichloromethane, constant potential of-2.94V (vs SCE), 4 hours of reaction time, and the reaction results are shown in Table 1.
After the reaction was completed, the catalyst 1 was reused, and a stability test was performed, wherein the reaction time was 4 hours each time, and other reaction conditions were the same as those of the initial reaction, and the reaction results are shown in Table 2.
From the methane yield of Table 1, it can be seen that copper cobaltate (CuCo 2 O 4 ) Is obviously superior to copper cobaltate (CuCo) with other shapes 2 O 4 ) And it was found from the stability test of Table 2 that copper cobaltate (CuCo) 2 O 4 ) And simultaneously has excellent stability. The specific surface area experiments of Table 3 also found that copper cobaltate (CuCo 2 O 4 ) Has the highest specific surface area.
Example 2:
the difference from example 1 is that: the hydrothermal reaction temperature in step (3) was 140℃and the resulting material was designated as catalyst 2, and the reaction results are shown in Table 1.
Example 3:
the difference from example 1 is that: the temperature of the hydrothermal reaction in step (3) was 170℃and the resulting material was designated as catalyst 3, and the reaction results are shown in Table 1.
Example 4:
the difference from example 1 is that: the hydrothermal reaction time in step (3) was 12 hours, and the obtained material was named as catalyst 4, and the reaction results are shown in Table 1.
Example 5:
the difference from example 1 is that: the hydrothermal reaction time in the step (3) was 24 hours, the obtained material was named as catalyst 5, the reaction results are shown in Table 1,
comparative example 1:
the difference from example 1 is that: the temperature of the hydrothermal reaction in the step (3) is 120 ℃, the obtained material is named as a catalyst 6, the reaction results are shown in Table 1, and the morphology electron microscope chart is shown in FIG. 4.
Comparative example 2:
the difference from example 1 is that: NH in step (1) 4 The amount of F was 0g, the obtained material was designated as catalyst 7, the reaction results are shown in Table 1, and the morphology electron microscope chart is shown in FIG. 5.
Comparative example 3:
the difference from example 1 is that: NH in step (1) 4 The amount of F was 0.0889g, the obtained material was designated as catalyst 8, the reaction results are shown in Table 1, and the morphology electron microscope chart is shown in FIG. 6.
TABLE 1
TABLE 2
| Number of repetitions | 1 | 2 | 3 | 4 | 5 | 6 |
| Methane yield (mu mol) | 148.83 | 145.11 | 144.81 | 141.89 | 145.87 | 142.88 |
TABLE 3 Table 3
| Material | S BET a (m 2 /g) |
| CuCo 2 O 4 -1 | 34.63 |
| CuCo 2 O 4 -6 | 42.37 |
| CuCo 2 O 4 -7 | 39.90 |
| CuCo 2 O 4 -8 | 61.03 |
Claims (6)
1. The application of spinel type catalyst in dechlorination reaction of electro-catalytic reduction dichloromethane is characterized in that the catalyst is CuCo 2 O 4 Bimetallic spinel, cuCo 2 O 4 The bimetallic spinel is a rod-shaped nano structure with bulges on the surface;
the catalyst is prepared by a hydrothermal method, and the hydrothermal method comprises the following steps:
1) Copper salt, cobalt salt, urea and NH 4 F are sequentially dissolved in deionized water to obtain a solution A, wherein copper salt, cobalt salt, urea and NH in the solution A 4 F is in a molar ratio of 1:2:10:6;
2) Uniformly stirring the solution A, and performing hydrothermal reaction at 140-170 ℃ for 6-24 hours to obtain a solution B;
3) Alternately cleaning the solution B with deionized water and ethanol, centrifuging and drying to obtain a solid I;
4) Calcining the solid I in air at 350-450 ℃ for 3-12 hours to obtain the catalyst.
2. The use according to claim 1, wherein the diameter of the rod-like nanostructure is 200-300 nm, and the specific surface area of the catalyst is 30-100 m 2 /g。
3. The use according to claim 1, wherein in step 1) the copper and cobalt salts are Cu (NO 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O; in the step 2), stirring time is 30-60 min; in the step 3), the cleaning times are 6-10 times, the drying temperature is 60-80 ℃, and the drying time is 12-24 hours; in the step 4), the temperature rising rate during calcination is 1-5 ℃/min.
4. The use according to claim 1, wherein the reaction is carried out in a three-electrode single-chamber electrolytic cell reactor system; the bimetallic spinel catalyst is loaded on the working electrode of the electrolytic cell; the load is 0.5-2.0 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The working electrode is a carbon cloth electrode.
5. The use according to claim 4, wherein the anode of the three-electrode single-chamber electrolytic cell is a Pt-plate electrode and the reference electrode is Ag/AgCl/Me 4 NCl, the electrode solution is N, N-dimethylformamide and acetonitrile, and the volume ratio of the N, N-dimethylformamide to the acetonitrile is 3:1.
6. The use according to claim 4, wherein the cell system electrolyte is a DMF solution; the concentration of the electrolyte tetrabutylammonium tetrafluoroborate is 0.1-0.5 mol/L; the addition amount of the electrolyte is 50-100 mL; the concentration of dichloromethane in the electrolyte is 0.01-0.1 mol/L; the constant potential is-2.14 to V to-2.94 to V (vs SCE).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074133A (en) * | 2007-05-14 | 2007-11-21 | 浙江衢化氟化学有限公司 | Antichloration of hydrocarbon chloride in waste water |
| CN106824196A (en) * | 2016-12-30 | 2017-06-13 | 浙江大学 | A kind of catalyst peculiar to vessel of soot and nitrogen oxides cooperation-removal and preparation method thereof |
| CN107790116A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院福建物质结构研究所 | The preparation of spinel catalyst and the elimination applied to nitrogen oxides |
| CN109148160A (en) * | 2018-08-06 | 2019-01-04 | 安徽师范大学 | A kind of core-shell structure manganese cobalt/cobalt oxide@nickel cobalt oxide composite material and preparation method and application |
| CN111135658A (en) * | 2019-12-25 | 2020-05-12 | 宁波鸿朗环保科技有限公司 | Organic waste gas catalytic combustion comprehensive treatment system containing Cl-VOCs |
-
2022
- 2022-01-25 CN CN202210090440.5A patent/CN114433091B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074133A (en) * | 2007-05-14 | 2007-11-21 | 浙江衢化氟化学有限公司 | Antichloration of hydrocarbon chloride in waste water |
| CN107790116A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院福建物质结构研究所 | The preparation of spinel catalyst and the elimination applied to nitrogen oxides |
| CN106824196A (en) * | 2016-12-30 | 2017-06-13 | 浙江大学 | A kind of catalyst peculiar to vessel of soot and nitrogen oxides cooperation-removal and preparation method thereof |
| CN109148160A (en) * | 2018-08-06 | 2019-01-04 | 安徽师范大学 | A kind of core-shell structure manganese cobalt/cobalt oxide@nickel cobalt oxide composite material and preparation method and application |
| CN111135658A (en) * | 2019-12-25 | 2020-05-12 | 宁波鸿朗环保科技有限公司 | Organic waste gas catalytic combustion comprehensive treatment system containing Cl-VOCs |
Non-Patent Citations (2)
| Title |
|---|
| Label-free detection of exosomes based on ssDNA-modulated oxidase-mimicking activity of CuCo2O4 nanorods;Yingzhi Zhang 等;Analytica Chimica Acta;第1145卷;摘要，正文3.1、3.3、4，Fig. 1，Scheme 1 * |
| Yingzhi Zhang 等.Label-free detection of exosomes based on ssDNA-modulated oxidase-mimicking activity of CuCo2O4 nanorods.Analytica Chimica Acta.2021,第1145卷摘要，正文3.1、3.3、4，Fig. 1，Scheme 1. * |
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