CN115193431A - Delta-MnO 2 /AC composite catalyst, preparation method and application thereof - Google Patents
Delta-MnO 2 /AC composite catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000011572 manganese Substances 0.000 claims abstract description 59
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001354 calcination Methods 0.000 claims abstract description 46
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000005949 ozonolysis reaction Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010043515 Throat cancer Diseases 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 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 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 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
- 238000003980 solgel method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009423 ventilation Methods 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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Abstract
The invention discloses delta-MnO 2 A/AC composite catalyst, a preparation method and an application thereof. Delta-MnO of the present invention 2 The preparation method of the/AC composite catalyst comprises the following steps: firstly, the activated carbon carrier is soaked in KMnO 4 In the solution, after full reaction, a catalyst precursor is obtained, and then the catalyst precursor is calcined in the air atmosphere to obtain delta-MnO 2 a/AC composite catalyst; the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1 (2-20); in S2The calcining temperature is 200-450 ℃, and the calcining time is 0.1-12 h. delta-MnO prepared by the above preparation method 2 the/AC composite catalyst has excellent catalytic activity and humidity resistance, and can keep good ozone decomposition rate for a long time under the condition of a large humidity range (0-90%).
Description
Technical Field
The invention relates to the technical field of metal oxide catalysts, in particular to delta-MnO 2 a/AC composite catalyst, a preparation method and application thereof.
Background
Ozone pollution is the most prominent air pollution problem in the world in recent years, and ozone with too high concentration can not only oxidize articles and reduce the service life of the articles, but also enter the room through the effects of ventilation, diffusion and the like, thereby causing serious harm to human health. Studies have shown that ozone induces various diseases such as throat cancer, so that in recent years, control and elimination of ozone pollution have been receiving great attention, and ozone control is urgently needed.
At present, the ozone treatment mainly adopts a catalytic decomposition method, and the used catalyst mainly comprises a supported catalyst and a metal oxide catalyst, wherein the supported catalyst generally refers to a catalyst obtained by loading an active component on a carrier with stable structure and high specific surface area; the metal oxide catalyst mainly includes noble metal and transition metal oxide catalysts. Compared with the high cost of a noble metal catalyst, the transition metal oxide catalyst is a relatively cheap ozonolysis catalyst, and particularly, the manganese oxide catalyst is widely applied to the field of ozonolysis due to the characteristics of low price, easily available materials, excellent catalytic performance and the like.
For example, the prior art discloses a high-efficiency moisture-resistant ozone decomposition catalyst and a preparation method thereof, wherein a sol-gel method is adopted to prepare a manganese, copper, nickel and cobalt oxide full-active component catalyst, the activity of the catalyst is improved by adding citric acid, the moisture resistance of the catalyst is improved by adding a cationic surfactant and controlling the pH value, but the preparation method is complex, the prepared catalyst is greatly influenced by the environmental humidity, water molecules and ozone molecules compete to adsorb on active sites, the catalyst is rapidly inactivated, and the moisture resistance of the ozone decomposition catalyst needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defect and the defect of poor ozone decomposition effect of the existing manganese oxide catalyst in a high-humidity environment, and provides delta-MnO 2 Preparation method of/AC composite catalyst, in-situ reduction KMnO using active carbon as carrier 4 Active component precursor, then calcining in air atmosphere to regulate MnO 2 The crystal form of (2) increases the number of surface oxygen vacancies and reduces competitive adsorption of water, thereby improving the hydrophobicity and catalytic activity of the prepared catalyst and further improving the ozone decomposition effect of the catalyst in a high-humidity environment.
Another object of the present invention is to provide a delta-MnO 2 a/AC composite catalyst.
It is still another object of the present invention to provide delta-MnO 2 The application of the/AC composite catalyst in decomposing ozone.
The above purpose of the invention is realized by the following technical scheme:
Delta-MnO 2 The preparation method of the/AC composite catalyst comprises the following steps:
s1, dipping an activated carbon carrier in KMnO 4 In the solution, after full reaction, drying and removing water to obtain a catalyst precursor;
s2, calcining the catalyst precursor in the S1 in an air atmosphere to obtain delta-MnO 2 a/AC composite catalyst;
the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, the mass ratio of the manganese active component to the active carbon carrier is 1 (2-20), and the manganese active component is amorphous;
the temperature of the calcination treatment in the S2 is 200-450 ℃, and the calcination treatment time is 0.1-12 h.
The invention takes active carbon as a carrier and KMnO 4 Reaction to form amorphous MnO 2 Then calcining under specific conditions to obtain delta-MnO 2 a/AC composite catalyst. The inventors found that the atmosphere of the calcination treatment was to MnO 2 The crystal form has obvious influence, and the crystal form can be prepared in a humid environment only by calcining in an air atmosphere and regulating and controlling corresponding calcining temperature and calcining timeDelta-MnO of high Activity for ozonolysis 2 A crystalline form; and the content of the manganese active component is too low, so that the ozone decomposition active sites formed by calcination are limited, and the ozone decomposition rate is reduced; too high a manganese content not only leads to delta-MnO 2 The particles are agglomerated, so that the dispersity of the particles is reduced, and the number of active sites is reduced; but also block the pore structure of the catalyst, increase the airflow resistance and be not beneficial to the decomposition of ozone. In addition, too low a calcination temperature or too short a calcination time cannot make amorphous MnO 2 Conversion to highly crystalline delta-MnO 2 Resulting in fewer catalytically active sites and thus a reduced ozone decomposition rate. The calcination temperature is too high or the calcination time is too long, which not only leads the activated carbon carrier to be coated with O in the air 2 Oxidation, resulting in loss of support of the manganese active component, reduced specific surface area, increased delta-MnO 2 Can also result in amorphous MnO 2 Phase change to Mn 2 O 3 Thereby reducing delta-MnO 2 Ozone decomposition performance of the/AC composite catalyst.
Specifically, the activated carbon may be subjected to ultrasonic treatment to remove surface impurities thereof before the impregnation treatment.
Preferably, the temperature of the calcination treatment in S2 is 350-400 ℃, and the calcination treatment time is 3-6 h.
Preferably, the mass ratio of the manganese active component to the activated carbon carrier in S1 is 1 (2-10).
In a specific embodiment, the KMnO in step S1 of the present invention 4 The concentration of the solution is 0.1-1 mol/L.
In a specific embodiment, the drying temperature in step S1 of the present invention is 60 to 120 ℃, and the drying time is 1 to 24 hours.
The invention also discloses delta-MnO 2 Delta-MnO prepared by preparation method of/AC composite catalyst 2 a/AC composite catalyst.
Specifically, the delta-MnO 2 The average pore diameter of the/AC composite catalyst is more than or equal to 2.20nm, and the larger average pore diameter can inhibit the water vapor in the humid environment from condensing in the pore channel of the catalyst when decomposing ozone, and reduce the airflow resistance, thereby promoting the ozone diffusion and the mass transfer rate, and the method comprises the following stepsThe full contact between ozone and the active sites of the catalyst is facilitated, and the hydrophobic property of the catalyst is improved to a certain degree.
Delta-MnO 2 The application of the/AC composite catalyst in decomposing ozone is also within the protection scope of the invention.
Preferably, the delta-MnO 2 The environmental humidity of the application of the/AC composite catalyst in decomposing ozone is 0-90%.
Preferably, the delta-MnO 2 The environmental humidity of the application of the/AC composite catalyst in decomposing ozone is 50-90%.
Delta-MnO of the present invention 2 the/AC composite catalyst has good ozone decomposition effect in a low-humidity environment (the environmental humidity is 10%), even under a high-humidity condition (the environmental humidity is more than or equal to 50%), because the condensation of water vapor is reduced due to the hydrophobicity and the proper pore structure of the active carbon, the competitive adsorption of water molecules is reduced, and the catalytic activity of the catalyst in the high-humidity environment is improved.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides delta-MnO 2 The preparation method of the/AC composite catalyst takes activated carbon as a carrier and KMnO 4 Active component precursor, manganese-loaded active component is reduced in situ by using active carbon, and MnO is regulated and controlled through specific calcination treatment 2 The crystal form simultaneously utilizes the hydrophobicity of the activated carbon carrier, thereby leading to the preparation of delta-MnO 2 the/AC composite catalyst has excellent catalytic activity and moisture resistance, so that the catalyst has excellent catalytic activity in a humid environment, and can maintain the ozone decomposition rate of more than 80% for a long time under the condition of a large humidity range (0-90%).
Drawings
FIG. 1 is XRD patterns of Activated Carbon (AC), catalyst precursor (Mn/AC) in step S1, catalyst in example 1 (Mn/AC-A), catalyst in comparative example 1 (Mn/AC-N), and catalyst in comparative example 2 (Mn/AC-H).
FIG. 2 is SEM, TEM and HRTEM images of Activated Carbon (AC), catalyst in example 1 (Mn/AC-A) and catalyst in comparative example 1 (Mn/AC-N).
FIG. 3 is an EDS diagram of the catalyst (Mn/AC-A) in example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
Delta-MnO 2 The preparation method of the/AC composite catalyst comprises the following steps:
s1, impregnating an activated carbon carrier in KMnO 4 Fully soaking in the solution, and drying to remove water to obtain a catalyst precursor;
s2, calcining the catalyst precursor in the S1 in an air atmosphere to obtain delta-MnO 2 a/AC composite catalyst;
wherein, the KMnO in S1 4 The concentration of the solution is 0.1mol/L;
the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1;
the calcining temperature in the S2 is 350 ℃, and the calcining time is 3h.
Example 2
Delta-MnO 2 A method for preparing an/AC hybrid catalyst, comprising substantially the same steps as in example 1, except that: the KMnO in S1 4 The concentration of the solution is 1mol/L; the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1.
Example 3
Delta-MnO 2 A method for preparing a/AC composite catalyst, comprising substantially the same steps as in example 1, except that: the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1.
Example 4
Delta-MnO 2 A method for preparing an/AC hybrid catalyst, comprising substantially the same steps as in example 1, except that: the catalyst precursor in S1 is composed of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1.
Example 5
Delta-MnO 2 A method for preparing a/AC composite catalyst, comprising substantially the same steps as in example 1, except that: the calcining temperature in the S2 is 400 ℃, and the calcining time is 6h.
Example 6
Delta-MnO 2 A method for preparing an/AC hybrid catalyst, comprising substantially the same steps as in example 1, except that: the calcining treatment temperature in the S2 is 200 ℃, and the calcining treatment time is 12h.
Example 7
Delta-MnO 2 A method for preparing an/AC hybrid catalyst, comprising substantially the same steps as in example 1, except that: the calcining temperature in the S2 is 450 ℃, and the calcining time is 0.1h.
Comparative example 1
MnO (MnO) x The preparation method of the/AC composite catalyst comprises the following steps:
s1, impregnating an activated carbon carrier in KMnO 4 Fully soaking in the solution, and drying to remove water to obtain a catalyst precursor;
s2, calcining the catalyst precursor in the S1 in a nitrogen atmosphere to obtain delta-MnO 2 a/AC composite catalyst;
wherein, the KMnO in S1 4 The concentration of the solution is 0.1mol/L;
the catalyst precursor in S1 is composed of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1;
the calcining temperature in the S2 is 350 ℃, and the calcining time is 3h.
Comparative example 2
MnO (MnO) x Preparation of/AC composite catalystThe method comprises the following steps:
s1, impregnating an activated carbon carrier in KMnO 4 Fully soaking in the solution, and drying to remove water to obtain a catalyst precursor;
s2, calcining the catalyst precursor in the S1 in a hydrogen atmosphere to obtain delta-MnO 2 a/AC composite catalyst;
wherein, the KMnO in S1 4 The concentration of the solution is 0.1mol/L;
the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, and the mass ratio of the manganese active component to the active carbon carrier is 1;
the calcining temperature in the S2 is 350 ℃, and the calcining time is 3h.
Result detection
Delta-MnO obtained in examples 1 to 7 2 catalyst/AC composite and MnO prepared in comparative examples 1 to 2 x The structure representation and performance test of the/AC composite catalyst are respectively carried out.
(1) XRD test
As can be seen from FIG. 1, the XRD diffraction pattern of the catalyst precursor (Mn/AC) in step S1 of the present invention substantially coincides with that of Activated Carbon (AC), thereby illustrating MnO in the catalyst precursor of the present invention 2 The catalyst (Mn/AC-A) prepared in example 1 had se:Sub>A structure of an amorphous form and se:Sub>A catalytically active component of deltse:Sub>A-MnO 2 In contrast, in the catalyst (Mn/AC-N) prepared in comparative example 1 and the catalyst (Mn/AC-H) prepared in comparative example 2, both of the catalytically active components were Mn 3 O 4 It is stated that delta-MnO favoring ozonolysis can be obtained only by calcination in an air atmosphere 2 A crystal form. The XRD patterns of the catalysts of examples 2-7 were substantially the same as that of Mn/AC-A of example 1.
(2) BET test
According to the BET test of the Activated Carbon (AC), the catalyst (Mn/AC-A) in example 1 and the catalyst (Mn/AC-N) in comparative example 1, the specific surface arese:Sub>A, the pore volume and the average pore diameter are shown in Table 1, and it can be seen that compared with the activated carbon alone, the specific surface areas of the catalyst Mn/AC-A and the catalyst Mn/AC-N are slightly reduced, but the pore volume and the average pore diameter are increased, particularly the average pore diameter of the catalyst Mn/AC-A reaches 2.20nm, and the increase of the average pore diameter can inhibit water vapor from condensing in se:Sub>A pore channel of the catalyst when ozone is decomposed in se:Sub>A humid environment, so that the airflow resistance is reduced, the ozone diffusion and mass transfer rate are promoted, the full contact of ozone and the catalyst active sites is facilitated, and the hydrophobic performance of the catalyst is improved to se:Sub>A certain extent. The specific surface arese:Sub>A, pore volume and average pore diameter of the catalysts of examples 2 to 7 were at substantially the same level as the datse:Sub>A relating to Mn/AC-A in example 1.
TABLE 1
| Sample(s) | Specific surface area (m) 2 g -1 ) | Pore volume (cm) 3 g -1 ) | Average pore diameter (nm) |
| AC | 878 | 0.04 | 1.95 |
| Mn/AC-N | 738 | 0.10 | 2.17 |
| Mn/AC-A | 682 | 0.12 | 2.20 |
(3) SEM and TEM testing
Fig. 2a, 2b and 2c are SEM, TEM and HRTEM images, respectively, of Activated Carbon (AC), as can be seen that the activated carbon surface is smooth and no significant lattice fringes are found. FIGS. 2d, 2e and 2f are SEM, TEM and HRTEM images of the catalyst (Mn/AC-N) in comparative example 1, respectively, and it can be seen that Mn/AC-N is a nano-coiled sheet structure and the lattice spacings thereof are respectively assigned to Mn at 0.48nm, 0.27nm and 0.24nm 3 O 4 Crystal plane (101), (103) and (211) of (A), which indicates that the active component of the catalyst in Mn/AC-N is Mn 3 O 4 Exist in the form of (1). FIGS. 2g, 2h and 2i are SEM, TEM and HRTEM images of the catalyst (Mn/AC-A) in example 1, respectively, and it can be seen that Mn/AC-A is se:Sub>A stacked layered structure and lattice spacings of 0.64nm, 0.25nm and 0.24nm are ascribed to deltse:Sub>A-MnO 2 (001), crystal plane (200) and crystal plane (110) of the Mn/AC-A catalyst, which indicates that the active component of the Mn/AC-A catalyst is deltse:Sub>A-MnO 2 The method further shows that the calcining atmosphere is closely related to the crystal form of the catalytic active component in the prepared catalyst, and the result is consistent with the XRD result.
(4) EDS testing
The catalyst of example 1 was subjected to energy dispersive X-ray spectroscopy (EDS) surface scan mapping, and the results are shown in FIG. 3, in which FIG. 3a is the catalyst of example 1, and FIGS. 3b, 3C, 3d and 3e correspond to the distribution of C, O, mn and K elements in the catalyst, respectively, and thus it can be seen that C, O, K and Mn elements are uniformly distributed, further proving that delta-MnO 2 Highly evenly dispersed on the AC surface, so that the active sites are more fully exposed, contact between ozone and the active sites is facilitated, and the ozone decomposition performance of the catalyst is improved.
(5) Decomposition of ozone test in different humidities
The catalysts prepared in examples 1 to 7 and comparative examples 1 to 2 and commercial ozonolysis catalysts (the active component manganese content is more than 85%) were subjected to the ozonolysis activity test.
The specific test method comprises the following steps: the different catalysts are respectively placed in a glass tube reactor, the dosage of the catalyst is 0.5g, and the reaction is carried out under the conditions of normal temperature and normal pressure. The flow rate of the reaction gas (ozone) is 1L/min, air is balance gas, the concentration of the inlet ozone is 40ppm, the humidity (10%, 50% and 90%) of the reaction system is adjusted by an air bubbling method, then an ozone analyzer is used for carrying out long-time (6 h) test analysis on the concentration of the gas after reaction, and the ozone decomposition rate after long-time decomposition is recorded.
Ozonolysis rate (%) = (C) in -C out )/C in X 100% where C in Is the inlet concentration of ozone, C out Is the ozone outlet concentration.
TABLE 2 ozone decomposition rates of examples and comparative examples and commercial ozone decomposition catalysts in different humidity environments
Delta-MnO of the invention 2 the/AC composite catalyst has the ozone decomposition rate of 83-96% when the ambient humidity is 10%, the ozone decomposition rate of 83-96% when the ambient humidity is 50%, and the ozone decomposition rate of 80-93% when the ambient humidity is 90%. While the catalysts obtained by calcination in a nitrogen atmosphere in comparative example 1 exhibited decomposition rates for ozone of 70%, 78% and 75% at ambient humidities of 10%, 50% and 90%, respectively; the catalyst obtained by calcination in a hydrogen atmosphere in comparative example 2 had decomposition rates for ozone of 73%, 80% and 79% at ambient humidities of 10%, 50% and 90%, respectively; the commercial ozone decomposition catalyst has the decomposition rates of 71%, 50% and 42% on ozone when the ambient humidity is 10%, 50% and 90%, so that the decomposition effects of different calcination treatment atmospheres direct catalysts on ozone in a humid environment are the same under other conditions, and compared with a hydrogen and nitrogen calcination atmosphere, the catalyst prepared in the air calcination atmosphere has better effect on ozone in a humid environmentThe catalytic activity of (3).
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. Delta-MnO 2 The preparation method of the/AC composite catalyst is characterized by comprising the following steps:
s1, dipping an activated carbon carrier in KMnO 4 In the solution, after full reaction, drying and removing water to obtain a catalyst precursor;
s2, calcining the catalyst precursor in the S1 in an air atmosphere to obtain delta-MnO 2 a/AC composite catalyst;
the catalyst precursor in S1 consists of a manganese active component and an active carbon carrier, the mass ratio of the manganese active component to the active carbon carrier is 1 (2-20), and the manganese active component is amorphous;
the temperature of the calcination treatment in the S2 is 200-450 ℃, and the calcination treatment time is 0.1-12 h.
2. The delta-MnO of claim 1 2 The preparation method of the/AC composite catalyst is characterized in that the calcining temperature in S2 is 350-400 ℃, and the calcining time is 3-6 h.
3. The delta-MnO of claim 2 2 The preparation method of the/AC composite catalyst is characterized in that the mass ratio of the manganese active component to the active carbon carrier in S1 is 1 (2-10).
4. The delta-MnO of claim 1 2 Preparation method of/AC composite catalystWherein the KMnO in S1 is 4 The concentration of the solution is 0.1-1 mol/L.
5. The delta-MnO of claim 1 2 The preparation method of the/AC composite catalyst is characterized in that the drying temperature in the S1 is 60-120 ℃, and the drying time is 1-24 h.
6. The delta-MnO of any one of claims 1 to 5 2 Delta-MnO prepared by preparation method of/AC composite catalyst 2 a/AC composite catalyst.
7. The delta-MnO of claim 6 2 a/AC hybrid catalyst, characterized in that said delta-MnO is 2 The average pore diameter of the mesoporous structure of the/AC composite catalyst is more than or equal to 2.20nm.
8. The δ -MnO of claim 6 2 The application of the/AC composite catalyst in decomposing ozone.
9. The delta-MnO of claim 8 2 The application of the/AC composite catalyst in decomposing ozone is characterized in that the applied environment humidity is 0-90%.
10. The delta-MnO of claim 9 2 The application of the/AC composite catalyst in decomposing ozone is characterized in that the applied environment humidity is 50-90%.
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| CN116371419A (en) * | 2023-04-21 | 2023-07-04 | 中南大学 | Microbial carbon-supported manganese-cobalt catalyst and preparation method and application thereof |
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