CN114425365B - Preparation method of defect-rich Mn-Co metal oxide catalyst - Google Patents
Preparation method of defect-rich Mn-Co metal oxide catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 37
- 229910018669 Mn—Co Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 7
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 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 12
- 238000001035 drying Methods 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
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- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
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- 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
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention discloses a preparation method of a defect-rich Mn-Co metal oxide catalyst, which comprises the following steps: synthesizing Mn/Co bimetallic MOFs precursor with coordination defects under the condition of high-energy ball milling, and calcining to obtain Mn-Co metal oxide rich in defects; the method has the advantages that the characteristics that metal ion agglomeration can be inhibited by taking MOFs as a catalyst precursor and the thought of constructing material defects by a mechanochemical method are utilized, the Mn/Co bimetallic MOFs precursor prepared by high-energy ball milling is calcined in air to form the Mn-Co metal oxide catalyst rich in defects, the MOFs with a large number of coordination defects have a special structure with short-range ordered and long-range disordered, the metal ion dispersibility is met, grains are refined, feasibility is provided for preparing the Mn-Co metal oxide rich in defects, the maximum specific surface area of the prepared catalyst can reach 85.8m 2/g, and the oxygen proportion of surface defects accounts for about 60% of oxygen species.
Description
Technical Field
The invention relates to the field of inorganic nano catalytic materials, in particular to a preparation method of a Mn-Co metal oxide catalyst rich in defects.
Background
Volatile organic compounds (Volatile organic compounds, VOCs) have become one of the major components of air pollutants, causing serious environmental and human health hazards. In view of energy saving and environmental friendliness, low-temperature oxidation of light alkane catalysts and process development are one of the research hotspots of industrial catalysis. Because noble metal catalysts are expensive, commercial applications are limited, and among metal oxide catalysts, mn-Co oxides with spinel structures are one of the most effective active species for activating and cleaving C-C bonds, C-H bonds, and have great application potential in the catalytic elimination of VOCs. However, different preparation methods and post-synthesis modification can have influence on the specific surface area, morphology, defect density and the like of the catalyst, so that the activity of the catalyst is determined. In recent years, defect engineering theory has been successfully applied to the catalytic field. Such as heat treatment to control grain size, etching, atomic doping, high energy ball milling, etc., to improve catalyst performance by structuring defects. Recent studies have found that the amorphous disordered structure exposes a large number of active sites to the surface, and even expands the reaction to the interior of the catalyst volume, greatly improving the catalytic activity. Thus, increasing the defect density per unit area of the catalyst has become a new break-through for improving the catalytic performance. The mechanochemical synthesis catalyst is gradually valued for its simple process, the ability to prepare amorphous or nanoscale particles, and the contribution to the fabrication of defects and pore structures. However, small-sized particles having high surface energy inevitably undergo hard agglomeration during heat treatment, which adversely affects the exposure of the active sites.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a Mn-Co metal oxide catalyst rich in defects, which uses MOFs as a catalyst precursor to inhibit agglomeration of metal ions, and uses a mechanochemical method to construct a material defect concept, wherein Mn/Co bimetallic MOFs precursor prepared by high-energy ball milling is calcined in air to form the Mn-Co metal oxide catalyst rich in defects.
The preparation method of the Mn-Co metal oxide catalyst rich in defects comprises the following steps: synthesizing Mn/Co bimetallic MOFs precursor with coordination defects under the condition of high-energy ball milling, and calcining to obtain Mn-Co metal oxide rich in defects;
Further, the method comprises the following steps:
a. Mixing 1,3, 5-benzene tricarboxylic acid, nitrate containing cobalt and manganese, formic acid and N, N-dimethylformamide, performing a degradation treatment, and performing a ball milling treatment;
b. centrifugally cleaning and filtering after ball milling treatment, drying the obtained solid powder to obtain mauve solid powder MC-BTC, and calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst;
Further, in the step a, the nitrate containing cobalt and manganese is Mn (NO 3)2·4H2 O and Co (NO 3)2·6H2 O, in molar ratio Mn (NO 3)2·4H2O∶Co(NO3)2·6H2 o=1:4 to 4:1;
In the step a, 1,3, 5-benzene tricarboxylic acid and nitrate containing cobalt and manganese are mixed and placed in a ball milling tank, then formic acid is dissolved in N, N-dimethylformamide and added into the ball milling tank, and finally triethylamine is added;
in the step b, after ball milling treatment, the product is centrifugally washed by N, N-dimethylformamide and absolute ethyl alcohol and then filtered, and the ball milling time is 25-35min;
6. the method for preparing a defect-rich mn—co metal oxide catalyst according to claim 5, wherein: in the step b, the drying temperature is 50-70 ℃ and the drying time is 1.5-2.5 hours;
In the step b, the calcination atmosphere is air, the calcination temperature is 300-500 ℃, the muffle furnace temperature rising rate is 4 ℃/min, and the heat preservation time is 1-3 hours.
The invention also discloses a defect-rich Mn-Co metal oxide catalyst, which is prepared by the preparation method of the defect-rich Mn-Co metal oxide catalyst.
The beneficial effects of the invention are as follows: the preparation method of the Mn-Co metal oxide catalyst rich in defects disclosed by the invention adopts the MOFs as a catalyst precursor to inhibit the agglomeration of metal ions and adopts the thought of constructing material defects by a mechanochemical method, the Mn/Co bimetallic MOFs precursor prepared by high-energy ball milling is calcined in air to form the Mn-Co metal oxide catalyst rich in defects, the MOFs with a large number of coordination defects have a special structure of short-range order and long-range disorder, the dispersibility of metal ions is met, grains are refined, feasibility is provided for preparing the Mn-Co metal oxide rich in defects, the maximum specific surface area of the prepared catalyst can reach 85.8m 2/g, and the proportion of oxygen with surface defects accounts for about 60% of oxygen species.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is an X-ray diffraction (XRD) spectrum of a sample of Mn-Co metal oxide obtained, wherein curve A, B, C, D, E corresponds to the XRD spectra of samples of example 1, example 2, example 3, example 4 and example 5, respectively;
FIG. 2 is a graph showing the activity curves of the prepared defect-rich Mn-Co metal oxide samples versus the catalytic oxidation of C 3H8, wherein A, B, C, D, E corresponds to the activity curves of the samples of example 1, example 2, example 3, example 4, and example 5, respectively;
FIG. 3 is an SEM photograph of a sample of a Mn-Co metal oxide rich in defects, which is a photograph of sample C of example 3.
FIG. 4 is an O1s XPS spectrum of the prepared defect-rich Mn-Co metal oxide samples, wherein A, B, C, D corresponds to the O1s XPS spectra of the samples of example 1, example 2, example 3 and example 4, respectively.
Detailed Description
Example 1
Mixing 0.1g Mn(NO3)2·4H2O,0.47g Co(NO3)2·6H2O,0.420g 1,3,5- benzene tricarboxylic acids, and placing in a ball milling tank. 160. Mu.L of formic acid was dissolved in 1mLN, N-dimethylformamide, and then the solution was transferred to a ball mill pot, mixed with solid powder to obtain a suspension, and 420. Mu.L of triethylamine was added to conduct deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibrating high-energy ball mill, wherein the ball milling reaction time is 30min. The product was centrifugally washed with N, N-dimethylformamide and absolute ethanol, then filtered, and the remaining solid powder was dried in a drying oven at 60℃for 2 hours, and calcined in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (A) having a sample BET specific surface area of 62.8m 2·g-1. The calcination atmosphere is air, the calcination temperature is 400 ℃, the temperature rising rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Example two
Mixing 0.2g Mn(NO3)2·4H2O,0.35g Co(NO3)2·6H2O,0.420g 1,3,5- benzene tricarboxylic acids, and placing in a ball milling tank. 160. Mu.L of formic acid was dissolved in 1mLN, N-dimethylformamide, and then the solution was transferred to a ball mill pot, mixed with solid powder to obtain a suspension, and 420. Mu.L of triethylamine was added to conduct deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibrating high-energy ball mill, wherein the ball milling reaction time is 30min. The product was centrifugally washed with N, N-dimethylformamide and absolute ethanol, then filtered, and the remaining solid powder was dried in a drying oven at 60℃for 2 hours, and calcined in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (B), with a sample BET specific surface area of 72.3m 2·g-1. The calcination atmosphere is air, the calcination temperature is 400 ℃, the temperature rising rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Example III
Mixing 0.3g Mn(NO3)2·4H2O,0.23g Co(NO3)2·6H2O,0.420g 1,3,5- benzene tricarboxylic acids, and placing in a ball milling tank. 160. Mu.L of formic acid was dissolved in 1mLN, N-dimethylformamide, and then the solution was transferred to a ball mill pot, mixed with solid powder to obtain a suspension, and 420. Mu.L of triethylamine was added to conduct deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibrating high-energy ball mill, wherein the ball milling reaction time is 30min. The product was centrifugally washed with N, N-dimethylformamide and absolute ethanol, then filtered, and the remaining solid powder was dried in a drying oven at 60℃for 2 hours, and calcined in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (C), with a sample BET specific surface area of 85.8m 2·g-1. The calcination atmosphere is air, the calcination temperature is 400 ℃, the temperature rising rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Example IV
Mixing 0.4g Mn(NO3)2·4H2O,0.12g Co(NO3)2·6H2O,0.420g 1,3,5- benzene tricarboxylic acids, and placing in a ball milling tank. 160. Mu.L of formic acid was dissolved in 1mLN, N-dimethylformamide, and then the solution was transferred to a ball mill pot, mixed with solid powder to obtain a suspension, and 420. Mu.L of triethylamine was added to conduct deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibrating high-energy ball mill, wherein the ball milling reaction time is 30min. The product was centrifugally washed with N, N-dimethylformamide and absolute ethanol, then filtered, and the remaining solid powder was dried in a drying oven at 60℃for 2 hours, and calcined in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (D), with a sample BET specific surface area of 76.3m 2·g-1. The calcination atmosphere is air, the calcination temperature is 400 ℃, the temperature rising rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Comparative experiments
Mixing 0.3g Mn (NO 3)2·4H2O,0.23g Co(NO3)2·6H2 O,0.08g NaOH solid and placing in a ball milling tank, screwing the ball milling tank, fixing the ball milling tank in a clamping groove of a vibrating high-energy ball mill, centrifugally cleaning a product by using absolute ethyl alcohol for 30min, filtering, drying the rest solid powder in a drying box at 60 ℃ for 2 hours, calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (E), wherein the BET specific surface area of a sample is 60.6m 2·g-1, the calcining atmosphere is air, the calcining temperature is 400 ℃, the temperature rising rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Test example 1:
XRD tests were performed on A, B, C, D and E samples of each example, respectively, and the test results are shown in FIG. 1, wherein the phase structures of A, B, C, D, E samples are Co 3O4-Mn3O4 composite oxides, E samples show higher crystallinity, and A, B, C, D samples show lower crystallinity, and the crystal grains of the catalyst are thinner.
Test example 2:
The catalytic oxidation activity evaluation test of C 3H8 was performed on A, B, C, D and E samples in each example on a fixed bed reactor system. A catalyst of 0.9g quartz sand mixed with 50mg was placed in a quartz tube reactor, with quartz sand and quartz wool on both sides. The total flow of the reaction gas was 100mL min-1(1mL min-1C3H8、89mL min-1N2、10mL min-1O2), mass space velocity was 120000ml g -1h-1. The reaction temperature is controlled by a thermocouple, the temperature measuring device can timely detect the temperature of the fixed bed, and the temperature rising rate is 10 ℃ min -1; the concentration of C 3H8 after the mixed gas passed through the catalyst was detected on line using gas chromatography.
Test example 3:
Scanning Electron Microscope (SEM) testing was performed on sample C of example 3, and the results are shown in fig. 3 as SEM pictures at 30000 x magnification of the sample. From the figure, the catalyst obtained is porous and has a flocculent shape.
Test example 4:
The results of XPS tests performed on the examples using deconvolution fitting are shown in FIG. 4, where O1s XPS can be divided into surface oxygen species around 530.1eV and lattice oxygen species around 531.5 eV. The surface oxygen species are easily separated from the crystal lattice to form vacancy defects, wherein the proportion of the surface defect oxygen of the C sample accounts for about 60% of the oxygen species, which is beneficial to the improvement of the catalytic performance.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (6)
1. A preparation method of a defect-rich Mn-Co metal oxide catalyst is characterized by comprising the following steps of: synthesizing Mn/Co bimetallic MOFs precursor with coordination defects under the condition of high-energy ball milling, and calcining to obtain Mn-Co metal oxide rich in defects; the method comprises the following steps:
a. 1,3, 5-benzene tricarboxylic acid, nitrate containing cobalt and manganese, formic acid and N, N-dimethylformamide are mixed and then subjected to a degradation treatment, and then subjected to a ball milling treatment, wherein the nitrate containing cobalt and manganese is Mn (NO 3)2·4H2 O and Co (NO 3)2·6H2 O, according to the molar ratio Mn (NO 3)2·4H2O：Co(NO3)2·6H2 O=1:4-4:1;
b. And after ball milling treatment, centrifugally cleaning and filtering, drying the obtained solid powder to obtain mauve solid powder MC-BTC, and calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst.
2. The method for preparing a defect-rich mn—co metal oxide catalyst according to claim 1, wherein: in the step a, firstly, 1,3, 5-benzene tricarboxylic acid and nitrate containing cobalt and manganese are mixed and placed in a ball milling tank, then formic acid is dissolved in N, N-dimethylformamide, and added into a 50 mL ball milling tank, and finally triethylamine is added.
3. The method for preparing a defect-rich mn—co metal oxide catalyst according to claim 1, wherein: in the step b, after ball milling treatment, the product is centrifugally washed by N, N-dimethylformamide and absolute ethyl alcohol and then filtered, and the ball milling time is 25-35min.
4. A method for preparing a defect-rich Mn-Co metal oxide catalyst according to claim 3, wherein: in step b, the drying temperature is 50-70 ℃ and the drying time is 1.5-2.5 hours.
5. The method for preparing a defect-rich mn—co metal oxide catalyst according to claim 4, wherein: in the step b, the calcining atmosphere is air, the calcining temperature is 300-500 ℃, the muffle furnace heating rate is 4 ℃/min, and the heat preservation time is 1-3 hours.
6. A defect-rich Mn-Co metal oxide catalyst characterized by: is prepared by the preparation method of the defect-rich Mn-Co metal oxide catalyst as claimed in any one of claims 1 to 5.
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