CN110302840B - MnO (MnO)2Preparation method and application of/Cu-Al-BTC ternary metal organic framework material - Google Patents
MnO (MnO)2Preparation method and application of/Cu-Al-BTC ternary metal organic framework material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229910017767 Cu—Al Inorganic materials 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000411 inducer Substances 0.000 claims abstract description 7
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- PKPQWDSIINFZNV-UHFFFAOYSA-L dichlorocopper;ethane-1,2-diamine Chemical compound [Cl-].[Cl-].[Cu+2].NCCN PKPQWDSIINFZNV-UHFFFAOYSA-L 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012697 Mn precursor Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 5
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000013461 design Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000001965 increasing effect Effects 0.000 description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- BXZCTOIDCRWONQ-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu+2].NCCN BXZCTOIDCRWONQ-UHFFFAOYSA-N 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
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Abstract
The invention belongs to the technical field of design and preparation of novel functional materials, and provides MnO2A preparation method and application of a/Cu-Al-BTC ternary metal organic framework material. The invention takes a microwave-assisted heating-dipping combination method as a synthesis method, selects a mixed solution of benzoic acid and acetic acid as a stabilizer, and takes dihydroxyl-bistetramethyl ethylenediamine copper (II) chloride, (octadecyl-9-alkenyl acetoacetato-O1', O3) dipropyl-2-alcoaluminum chloride as a metal salt to synthesize the Cu-Al precursor material with excellent physical and chemical properties. Thereafter, FMES and OP-6 were selected as molecular inducers to induce MnO2Enters the inside of the framework structure of a Cu-Al precursor material to prepare MnO with a ternary metal active site2a/Cu-Al-BTC catalyst. The material achieves 90-96% of denitration efficiency, and can keep the structure stable until 340 ℃.
Description
Technical Field
The invention relates to novel MnO2A preparation method of a/Cu-Al-BTC ternary metal organic framework material and application thereof in CO selective catalytic reduction denitration (CO-SCR) belong to the technical field of novel functional material design and preparation.
Background
Nitrogen oxide (NOx) emissions can form environmental pollution events such as acid rain, photochemical smog, etc., and pose serious hazards to human health and the ecological environment. Because the emission of NOx in China is not completely controlled at present, the pollution control and emission reduction of NOx are key problems to be solved in the environmental field of China at present. Among the NOx removal methods, Selective Catalytic Reduction (SCR) is currently the most widely used and most effective denitration technique. In SCR technology, NH is often used3,CO, H2And hydrocarbon and the like are used as reducing agents, wherein the CO-SCR technology has the advantages of long service life of a catalyst and capability of simultaneously removing CO and NOx pollutants, so that the research trend of the SCR technology is realized. For the CO-SCR technology, the development and selection of catalysts are the key to determine the denitration performance of the reaction. In terms of catalyst, the SCR catalyst mainly includes a noble metal catalyst, a molecular sieve catalyst, a metal oxide catalyst, and the like. However, the existing catalyst has the problems of high price, poor selectivity, poor stability and the like, so that the key scientific problem to be solved by the CO-SCR technology at present is to develop a novel catalyst with good denitration efficiency, strong selectivity, high thermal stability and low price.
In recent years, the emerging MOFs series of materials have been considered as an ideal SCR catalyst. The MOFs have the following advantages: the huge specific surface area can provide a reaction site for the reaction; the unsaturated metal sites can adsorb reaction gas and catalyze reaction; meanwhile, the adjustable topological structure can enhance the selectivity of the gas; has excellent thermal stability, and the characteristics lay a foundation for the MOFs material to catalyze the CO-SCR reaction. In MOFs, different metal central ions play different roles in the aspects of improving denitration efficiency, enhancing stability, reducing reaction temperature and the like. How to select and combine metal ions with different functions to enable the metal ions to be capable of synergistically catalyzing CO-SCR reaction and improving the performance of the catalyst is a research focus in the field of current MOFs material denitration.
Studies by Jiang et Al have shown that Cu-BTC has some SCR activity, while trivalent metal cations such as Al3+The ions may replace a portion of the Cu within the lattice of the material2+Thereby increasing the charge density of the material and further promoting the generation and uniform dispersion of metal active sites. Therefore, it is feasible to firstly select Cu and Al as metal central ions to synthesize the Cu-Al precursor material. The manganese-based oxide catalyst is proved to be capable of effectively reducing the activation temperature of the catalyst, so that the MOFs material containing the ternary metals of Cu, Al and Mn is probably a novel catalyst with better low-temperature activity and denitration efficiency. However, at present, the synthesis of MOFs materials has the following problems: the conventional hydrothermal method has the problems of high energy consumption and long time consumption; reported Cu-BTC MOFs often use nitrate as a source of metal ions, but have the problems of low yield, poor metal active site dispersibility, low catalytic efficiency and the like; homogeneous, stable, high catalytic activity MnO2The synthesis of the/Cu-Al-BTC ternary metal organic framework material and the CO-SCR application thereof have not been reported yet.
Disclosure of Invention
The invention uses a microwave-assisted heating-dipping combined method as a synthesis method, and uses a specific molecular inducer to induce MnO2The method provides a novel MnO for entering the interior of the MOFs framework structure as a design strategy2The design and preparation method of the/Cu-Al-BTC ternary metal organic framework material is applied to the technology of catalyzing CO-SCR denitration, and the material has the characteristics of uniformity, stability and high catalytic activity.
According to the invention, the Cu-Al precursor material is synthesized by adopting a microwave-assisted heating method, so that the problems of high energy consumption and long time consumption of a common hydrothermal method are effectively solved. In the synthesis process, a specific acidic solution is selected as a stabilizer for the first time, so that the performance quality of the synthesized material can be effectively improved. The method can realize the purposes of rapid and repeated synthesis, yield improvement and product selectivity enhancement, and is a high-efficiency synthesis method of MOFs materials.
In earlier researches, the deprotonation rate of commonly used raw materials such as copper nitrate, aluminum nitrate and the like in the reaction process is low, the synthesis rate of a Cu-Al precursor material is influenced, the yield of the material is low, and the dispersion of metal active sites of Cu and Al is not facilitated, so that the catalytic efficiency of the material is influenced. Therefore, through a large amount of experimental exploration, the method screens out specific long-chain metal Cu and Al salts, and effectively improves the synthesis efficiency of the Cu-Al precursor. Experimental results show that the method can enhance the interaction between Cu and Al metals, improve the dispersion degree of Cu and Al metal ions in the material and is beneficial to improving the catalytic performance of the material.
In addition, the researchers in this patent have further discovered that MnO is now being incorporated2In the preparation process of introducing the Cu-Al precursor, a specific surfactant is added as a molecular inducer, so that the dissolution and dispersion of the Mn precursor can be effectively promoted, Mn elements are fully induced to enter the Cu-Al precursor structure, and novel uniform, stable and high-catalytic MnO is finally synthesized2a/Cu-Al-BTC ternary metal organic framework compound.
The technical scheme of the invention is as follows:
MnO (MnO)2The preparation method of the/Cu-Al-BTC ternary metal organic framework material comprises the following steps:
(1) preparation of Cu-Al precursor
The trimesic acid H is reacted with3Dissolving BTC in a mixed solution of absolute ethyl alcohol, benzoic acid and acetic acid with a volume ratio of 25:3:2-35:4:1 to prepare a trimesic acid solution with a concentration of 0.16-0.18mol/L, and mixing and stirring the solution on a magnetic stirrer until the solution is dissolved; then adding dihydroxy-bistetramethyl ethylenediamine copper (II) chloride, octadecyl-9-alkenyl acetoacetato-O1', O3) dipropyl-2-alcoaluminum chloride and ultrapure water, and continuously stirring until the materials are completely dissolved; wherein the molar ratio of the copper salt to the aluminum salt to the trimesic acid is 6.78:1.24:4.8-1.32:1.24:7.2, and the volume ratio of the absolute ethyl alcohol to the ultrapure water is 0.71:1-1.4: 1; placing the mixed system in a microwave reactor, and reacting at 100-160 ℃ for 0.5-1.5h to obtain blue liquid; the reactant is centrifugally collected and is fed with absolute ethyl alcohol and ultrapure water in sequencePurifying; finally, vacuum drying the reactant to obtain a blue powdery solid;
(2) preparation of Mn precursor solution
Manganese chloride tetrahydrate (MnCl)2·4H2O) putting the solid in absolute ethyl alcohol, stirring until the solid is dissolved, and preparing into a manganese chloride solution with the Mn ion concentration of 0.14-0.34 mol/L; adding a mixed solution of two molecular inducers, namely methyl stearate polyoxyethylene ether sulfonate (FMES) and octyl phenol polyoxyethylene ether (OP-6), into the solution, and magnetically stirring for 0.5-1.5h at room temperature; wherein the molar ratio of FMES to OP-6 is 1:0.83-1:3.32, and the volume ratio of the manganese chloride solution to the inducer mixed solution is 3.33:1-6: 1;
(3)MnO2preparation of/Cu-Al-BTC
Adding a Cu-Al precursor material into the Mn precursor solution to prepare a solution with the concentration of 0.025-0.075g/mL, and magnetically stirring for 3-5h at room temperature; filtering the mixed solution, taking the filtered solid, placing the solid in an oven, setting the heating temperature to be 100 ℃ and 120 ℃, and heating for 8-12 h; taking out the solid sample after the solid sample is cooled to room temperature, and carrying out reaction at the temperature of 240 ℃ and 260 ℃ and N2Calcining the sample for 2-3h in a tube furnace under the atmosphere to prepare dark blue MnO2The powder sample of/Cu-Al-BTC.
In the step (1), the vacuum drying condition is 90-110 ℃ and 10-12 h.
MnO (MnO)2The application of the/Cu-Al-BTC ternary metal organic framework material in the aspect of CO selective catalytic reduction denitration (CO-SCR).
The invention has the beneficial effects that: the invention provides a method for preparing MnO by microwave-assisted heating-impregnation combination2The sample obtained by the method for preparing the/Cu-Al-BTC material has uniform particles, the particle size of about 0.2-0.5 mu m, complete appearance and specific surface area of 647m2g-1. The CO-SCR test result shows that MnO2the/Cu-Al-BTC catalyst achieves 90-96% of denitration efficiency within the temperature range of 260-375 ℃, has better low-temperature activity and higher thermal stability. The method has the advantages of short reaction time, low energy consumption and good catalytic effect, and is a novel, efficient and convenient preparation method of the MOFs catalyst.
Drawings
FIG. 1 shows MnO in different proportions2XRD pattern of/Cu-Al-BTC material;
FIG. 2 shows MnO in different proportions2SEM image of/Cu-Al-BTC material; (a) MnO2/Cu-Al-BTC(A), (b)MnO2/Cu-Al-BTC(B)；
FIG. 3 shows different ratios of MnO2N of/Cu-Al-BTC material2Sucking and removing the attached drawings;
FIG. 4 shows different ratios of MnO2TGA profile of/Cu-Al-BTC material;
FIG. 5 shows MnO2H of/Cu-Al-BTC catalyst2-a TPR map;
FIG. 6 shows different ratios of MnO2CO-SCR activity test curve of/Cu-Al-BTC catalyst.
Detailed Description
The following is a detailed description of the invention.
Example 1: preparation method of Cu-Al precursor material
4.8mmol of 1.0293g of trimesic acid (H) were taken3BTC) reagent, 25mL of absolute ethyl alcohol, 3mL of benzoic acid and 2mL of acetic acid are put into a 100mL beaker, and the beaker is placed on a magnetic stirrer to be mixed and stirred until being dissolved; 6.78mmol, 3.1488g dihydroxy-bistetramethyl ethylenediamine copper (II) chloride, 1.24mmol, 0.6159g (octadecyl-9-alkenyl acetoacetato-O1', O3) dipropyl-2-alcohol aluminum and 35mL ultrapure water are added into a beaker, and the mixture is placed on a magnetic stirrer to be mixed and stirred for 0.5h until the mixture is dissolved; placing the beaker filled with the mixed solution in a microwave reactor, reacting for 0.5h at 100 ℃, and after naturally cooling to room temperature, centrifugally collecting reactants, wherein the centrifugally collecting conditions are that the rotating speed is as follows: 9000r/min, time: and 5 min.
The collected samples were washed 3 times with 30mL of absolute ethanol and collected by centrifugation. The samples were then washed 3 times with 50mL of ultrapure water and collected by centrifugation each time. The collected sample was placed in a vacuum oven and dried at 90 ℃ for 10 hours to give a blue powdery solid.
Example 2: preparation method of Mn precursor solution
4.2mmol, 0.8312g of manganese chloride tetrahydrate are takenMnCl2·4H2O) solid is put into 30mL of absolute ethyl alcohol and placed on a magnetic stirrer to be mixed and stirred for 0.5h until the solid is dissolved, and a solution with the Mn ion concentration of 0.14mol/L is prepared. 5mL of a mixture of FMES and OP-6 was added to the solution at a molar ratio of 1:0.83, and the mixture was stirred at room temperature for 0.5 h.
Example 3: MnO2Synthesis method of/Cu-Al-BTC
0.3g of Cu-Al precursor material is mixed with 12ml of Mn precursor solution in a beaker, and the mixture is magnetically stirred for 3 hours at room temperature. Filtering the mixture, and heating the filtered solid at 100 deg.C for 8 hr. Taking out the solid sample after the solid sample is cooled to room temperature, and carrying out N treatment at 240 DEG C2Calcining the sample for 2h in a tube furnace under the atmosphere to obtain dark blue MnO2The powder sample of/Cu-Al-BTC.
Example 4:
in the embodiment 1 of the invention, the dosage of absolute ethyl alcohol, benzoic acid and acetic acid is respectively adjusted to 30mL, 3.5mL and 1.5mL, the dosage of trimesic acid is increased to 5.95mmol, the dosage of other raw materials and experimental steps are kept unchanged, and deep blue MnO is prepared2a/Cu-Al-BTC material.
Example 5:
in the embodiment 1 of the invention, the dosage of the absolute ethyl alcohol, the dosage of the benzoic acid and the dosage of the acetic acid are respectively adjusted to 35mL, 4mL and 1mL, the dosage of the trimesic acid is increased to 7.2mmol, the dosage of other raw materials and the experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 6:
in the inventive example 1, the dosages of dihydroxy-bistetramethylethylenediamine copper (II) chloride and (octadecyl-9-alkenyl acetoacetato-O1', O3) dipropyl-2-alcoaluminum were respectively adjusted to 3.88mmol and 1.24mmol, the dosage of ultrapure water was changed to 30mL, the microwave reaction temperature was increased to 130 ℃, the reaction time was increased to 1h, the vacuum drying temperature was increased to 100 ℃, the drying time was increased to 11h, the dosages of other raw materials and experimental steps were kept unchanged, and deep blue MnO was prepared2a/Cu-Al-BTC material.
Example 7:
in inventive example 1 ChlorinationThe dosages of dihydroxy-bistetramethyl ethylenediamine copper (II) and (octadecane-9-alkenyl acetoacetato-O1', O3) dipropane-2-alcohol aluminum are respectively adjusted to 1.32mmol and 1.24mmol, the dosage of ultrapure water is changed to 25mL, the microwave reaction temperature is increased to 160 ℃, the reaction time is increased to 1.5h, the vacuum drying temperature is increased to 110 ℃, the drying time is increased to 12h, the dosages of other raw materials and experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 8:
in the embodiment 2 of the invention, the dosage of manganese chloride tetrahydrate is increased to 7.2mmol, the dosage of the mixed solution of FMES and OP-6 is increased to 7mL, the molar ratio is changed to 1:2.08, the mixture is magnetically stirred for 1h at room temperature, the dosages of other raw materials and experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 9:
in the embodiment 2 of the invention, the dosage of manganese chloride tetrahydrate is increased to 10.2mmol, the dosage of the mixed solution of FMES and OP-6 is increased to 9mL, the molar ratio is changed to 1:3.32, the mixture is magnetically stirred for 1.5h at room temperature, the dosage of other raw materials and the experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 10:
in the embodiment 3 of the invention, the dosage of the Cu-Al precursor is increased to 0.6g, the magnetic stirring time is increased to 4h at room temperature, the dosages of other raw materials and experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 11:
in the embodiment 3 of the invention, the dosage of the Cu-Al precursor is increased to 0.9g, the magnetic stirring time is increased to 5h at room temperature, the dosage of other raw materials and experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 12:
in inventive example 3, the heating temperature was increased to 110 ℃ for 10 hours. When the tube furnace is used for calcination, the calcination temperature is increased to 250 ℃, the calcination time is increased to 2.5h, the use amount of other raw materials and experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Example 13:
in inventive example 3, the heating temperature was increased to 120 ℃ for 12 hours. When the tube furnace is used for calcination, the calcination temperature is increased to 260 ℃, the calcination time is increased to 3h, the use amount of other raw materials and experimental steps are kept unchanged, and the dark blue MnO is prepared2a/Cu-Al-BTC material.
Claims (3)
1. MnO (MnO)2The preparation method of the/Cu-Al-BTC ternary metal organic framework material is characterized by comprising the following steps of:
(1) preparation of Cu-Al precursor
The trimesic acid H is reacted with3Dissolving BTC in a mixed solution of absolute ethyl alcohol, benzoic acid and acetic acid with a volume ratio of 25:3:2-35:4:1 to prepare a trimesic acid solution with a concentration of 0.16-0.18mol/L, and mixing and stirring the solution on a magnetic stirrer until the solution is dissolved; then adding dihydroxy-bistetramethyl ethylenediamine copper (II) chloride, octadecyl-9-alkenyl acetoacetato-O1', O3) dipropyl-2-alcoaluminum chloride and ultrapure water, and continuously stirring until the materials are completely dissolved; wherein the molar ratio of the copper salt to the aluminum salt to the trimesic acid is 6.78:1.24:4.8-1.32:1.24:7.2, and the volume ratio of the absolute ethyl alcohol to the ultrapure water is 0.71:1-1.4: 1; placing the mixed system in a microwave reactor, and reacting at 100-160 ℃ for 0.5-1.5h to obtain blue liquid; centrifugally collecting the product, and purifying by using absolute ethyl alcohol and ultrapure water in sequence; finally, vacuum drying is carried out to obtain blue powdery solid;
(2) preparation of Mn precursor solution
Putting the manganese chloride tetrahydrate solid into absolute ethyl alcohol, stirring until the manganese chloride is dissolved, and preparing a manganese chloride solution with the Mn ion concentration of 0.14-0.34 mol/L; adding a mixed solution of two molecular inducers, namely methyl stearate polyoxyethylene ether sulfonate FMES and octyl phenol polyoxyethylene ether OP-6, into the solution, and magnetically stirring for 0.5-1.5h at room temperature; wherein the molar ratio of FMES to OP-6 is 1:0.83-1:3.32, and the volume ratio of the manganese chloride solution to the inducer mixed solution is 3.33:1-6: 1;
(3)MnO2preparation of/Cu-Al-BTC
Adding a Cu-Al precursor material into the Mn precursor solution to prepare a solution with the concentration of 0.025-0.075g/mL, and magnetically stirring for 3-5h at room temperature; filtering the mixed solution, taking the filtered solid, placing the solid in an oven, setting the heating temperature to be 100 ℃ and 120 ℃, and heating for 8-12 h; taking out the solid sample after the solid sample is cooled to room temperature, and carrying out reaction at the temperature of 240 ℃ and 260 ℃ and N2Calcining the sample for 2-3h in a tube furnace under the atmosphere to prepare dark blue MnO2The powder sample of/Cu-Al-BTC.
2. The method according to claim 1, wherein the vacuum drying is carried out at 90-110 ℃ for 10-12 hours in step (1).
3. MnO obtainable by the process according to claim 1 or 22The application of the/Cu-Al-BTC ternary metal organic framework material in the aspect of denitration of CO selective catalytic reduction reaction.
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| CN115888830A (en) * | 2022-07-08 | 2023-04-04 | 安徽工业大学 | Calcination-free octahedral Cu/Mn-BTC bimetallic MOF low-temperature SCR denitration catalyst, and preparation method and application thereof |
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