CN115487826A - Silver-doped manganese-cobalt hydrotalcite catalyst, preparation method thereof and method for degrading formaldehyde - Google Patents
Silver-doped manganese-cobalt hydrotalcite catalyst, preparation method thereof and method for degrading formaldehyde Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 32
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 32
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000000593 degrading effect Effects 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 121
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000012265 solid product Substances 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract 1
- 101710134784 Agnoprotein Proteins 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 102100024580 L-lactate dehydrogenase B chain Human genes 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 108010087599 lactate dehydrogenase 1 Proteins 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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Abstract
The invention discloses a silver-doped manganese-cobalt hydrotalcite catalyst, a preparation method thereof and a method for degrading formaldehyde; aiming at providing a preparation method of a silver-based manganese cobalt hydrotalcite catalyst and having higher degradation rate to formaldehyde; the technical scheme is as follows: (1) Preparing a mixed solution A of manganese nitrate, cobalt nitrate and silver nitrate; (2) Preparing NaOH and NaCO 3 The mixed alkali solution B of (1); (3) Reacting NH 4 Mixing the F and PVP to prepare solution C; (4) Simultaneously dropwise adding the solution A and the solution B into the solution C to obtain a uniform solution; (5) Uniformly stirring the uniform solution at 60 ℃ for 6 hours to obtain AgMnCo-LDH nanosheets; (6) Centrifuging the AgMnCo-LDH nanosheet solution, washing with deionized water, and drying to obtain a solid product AgMnCo-LDH; (7) The above solid product contains 5% of H 2 H of (A) to (B) 2 Further calcining in mixed gas of/ArFiring to obtain a finished product; belonging to the technical field of thermal catalytic materials and environmental protection.
Description
Technical Field
The invention relates to a catalyst, in particular to a silver-doped manganese-cobalt hydrotalcite catalyst, and also relates to a preparation method of the silver-doped manganese-cobalt hydrotalcite catalyst, belonging to the technical fields of thermal catalytic materials and environmental protection.
Background
Formaldehyde (HCHO) is one of the most serious indoor pollutants, mainly comes from widely used indoor decoration materials, is harmful to human health after long-term contact, and preparation of a high-efficiency stable catalyst to realize catalytic oxidation of formaldehyde at room temperature is always one of important research contents in the field of environmental catalysis. At present, a thermocatalytic reaction is considered as one of the most promising degradation reaction routes, wherein a noble metal supported catalyst has good formaldehyde oxidation efficiency, but has the problems of high price and the like, and relatively low-priced metals such as Ag, mn, co and the like have low activity. Therefore, it remains a challenge to develop low cost catalysts.
LDH is a two-dimensional anionic layered compound, a layered hydroxide composed of two or more metals, having abundant hydroxyl groups, has been widely studied as a thermal catalyst carrier, and Ni/Co-LDH catalysts have been synthesized by Jiang et al (Journal of Materials Science: materials in Electronics (2020) 31) 3500 to 3509) through a one-step hydrothermal method with a formaldehyde conversion rate of 99.7% at room temperature, and the synergy between a large amount of hydroxyl groups and Ni and Co ions is responsible for its superior activity. In recent years there have also been some Ag-based catalysts that catalyze the oxidation of formaldehyde. Chen et al (appl. Catal. B.282 (2021) 119543) found that the crystal structure of TiO2 carrier has great influence on the formaldehyde oxidation activity of Ag/TiO2 catalyst, and proposed that nonrenewable surface oxygen and silver oxide species provide active oxygen for formaldehyde conversion in low temperature environment, and metallic silver species are responsible for oxygen activation in high temperature range. Whereas silver-loaded octahedral molecular sieves (Ag/OMS-2-S) successfully prepared by Zhang et al (appl. Catal. B.2022, 303, 120875) by a solvent-free method completely oxidize formaldehyde at room temperature, and rich active oxygen is proposed to be a key factor influencing the activity of formaldehyde.
Although the formaldehyde oxidation catalyst prepared by the above method has good performance of catalyzing and degrading formaldehyde, it still faces some problems, such as high content of noble metal used, complex synthesis method, etc., which makes the manufacturing cost of the catalyst high and will be limited in practical application, so we need a catalyst with simple preparation method to degrade formaldehyde.
Disclosure of Invention
The invention aims to provide a preparation method of a silver-based manganese cobalt hydrotalcite catalyst based on the problems of the AgMnCo-LDH load type noble metal catalyst at present, and the silver-based manganese cobalt hydrotalcite catalyst has higher degradation rate on formaldehyde.
Therefore, the first technical scheme provided by the invention is as follows:
a preparation method of a silver-doped manganese-cobalt hydrotalcite catalyst sequentially comprises the following steps:
(1) Preparing a mixed solution A of manganese nitrate, cobalt nitrate and silver nitrate;
(2) Preparing NaOH and NaCO 3 The mixed alkali solution B of (1);
(3) Reacting NH 4 Mixing the F and the PVP to prepare a solution C;
(4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH =10 of the solution;
(5) Uniformly stirring the uniform solution at 60 ℃ for 6 hours to obtain an AgMnCo-LDH nanosheet solution;
(6) After the reaction is finished, centrifuging the AgMnCo-LDH nanosheet solution, washing with deionized water, and finally performing forced air drying to obtain a solid product AgMnCo-LDH, which is recorded as Ag/MC;
(7) The above solid product contains 5% of H 2 H of (A) to (B) 2 The mixture of/Ar is further calcined, and the obtained sample is represented as AgMnCoLDH-H and is recorded as Ag/MCL-H.
Further, in the preparation method of the silver-doped manganese cobalt hydrotalcite catalyst, the molar ratio of the manganese nitrate, the cobalt nitrate and the silver nitrate in the step (1) is 1: 1.0-3.0: 0.01-0.1.
Further, the preparation method of the silver-doped manganese cobalt hydrotalcite catalyst comprises the step (2) of adding NaOH and NaCO 3 The molar ratio of (A) to (B) is 0.5-1.0: 1.
Further, in the preparation method of the silver-doped manganese cobalt hydrotalcite catalyst, the concentration of NaOH in the step (4) is 1mol/L.
Further, in the preparation method of the silver-doped manganese cobalt hydrotalcite catalyst, the stirring speed in the step (5) is 200-2000r/min.
Further, in the preparation method of the silver-doped manganese cobalt hydrotalcite catalyst, the centrifugal parameters in the step (6) are as follows: 8000 turns/min for 5min; the washing conditions were: washing with deionized water for 3-5 times; the drying temperature is 80 ℃ and the drying time is 6-10 h.
Further, in the preparation method of the silver-doped manganese cobalt hydrotalcite catalyst, in the step (7), the calcination temperature is 100-300 ℃, and the calcination time is 2-6h.
The second technical scheme provided by the invention is that the silver-doped manganese cobalt hydrotalcite prepared by the method is catalyzed.
The method for catalyzing and degrading formaldehyde by using the catalyst comprises the following catalysis conditions: the concentration of formaldehyde is-35 ppm, the space velocity is 22 200mL/(g.h), and the reaction temperature is 30 ℃.
The AgMnCo-LDH catalyst provided by the invention is applied to the field of normal-temperature thermocatalysis. The catalyst has certain catalytic efficiency on monomer micromolecular organic matters, and can be used for degrading common organic pollutants in the air.
Compared with the prior art, the technical scheme provided by the invention has the following technical advantages:
(1) The lowest addition amount of Ag can reach 2w.t.%, so that the price of the noble metal is greatly reduced;
(2) The AgMnCo-LDH is subjected to hydrogen reduction treatment to obtain simple substance silver and rich active oxygen, so that the oxygen adsorption capacity of the AgMnCo-LDH is improved, and the formaldehyde degradation capacity is improved.
(3) The catalyst has the advantages of low preparation cost, simple and convenient preparation conditions, convenient operation and convenient large-scale production in industry.
Drawings
FIG. 1X-ray Crystal diffraction patterns (XRD) of Ag/LDH-H prepared in example 5 and comparative example 1;
FIG. 2 Scanning Electron Microscope (SEM) of Ag/LDH-H prepared in example 5;
FIG. 3 Scanning Electron Microscope (SEM) of Ag/LDH-H-S prepared in comparative example 1;
FIG. 4 Transmission Electron Microscopy (TEM) of Ag/LDH-H prepared in example 5;
FIG. 5 Transmission Electron Microscopy (TEM) of Ag/LDH-H-S prepared in comparative example 1;
Detailed Description
The following claims are presented to illustrate the invention in further detail in connection with the detailed description and the accompanying drawings, and should not be construed as limiting the invention in any way.
Example 1
The preparation method of the silver-based manganese cobalt hydrotalcite catalyst for thermal catalysis of formaldehyde degradation provided by the embodiment comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O)、5.8206g Co(NO 3 ) 2 ·6H 2 O and 0.1259g AgNO 3 Adding the solution into 30mL of deionized water, and marking as a solution A; (2) 0.8g of NaOH (1 mol/L) and 1.056g of Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 0.5g NH 4 Mixing the F and 1g of PVP to prepare a solution C; (4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH =10 of the solution; (5) Uniformly stirring the uniform solution at room temperature at 2000r/min for 6h to obtain 2AgMnCoLDH; (6) After the reaction is completed, centrifuging the 5AgMnCo-LDH solution, wherein the centrifugation parameters are as follows: 8000 revolutions/min for 5min, washing for 3 times by deionized water, and finally blowing and drying for 6h at 80 ℃ to obtain a solid product 2AgMnCo-LDH (abbreviated as 2 AgMCL); (7) The above solid product was calcined at 150 ℃ for 2 hours under an atmosphere of a H2/Ar mixed gas, and the obtained sample was expressed as 2AgMnCoLDH-H2 (abbreviated as 2 AgMCL-H2).
Example 2
The preparation method of the silver-based manganese cobalt hydrotalcite catalyst for thermal catalysis of formaldehyde degradation provided by the embodiment comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O)、5.8206g Co(NO 3 ) 2 ·6H 2 O and 0.3148g AgNO 3 Adding the solution into 30mL of deionized water, and marking as a solution A; (2) 0.8g of NaOH (1 mol/L) and 1.056g of Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 0.5g NH 4 Mixing the F and 1g of PVP to prepare a solution C; (4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH of the solution =10; (5) Uniformly stirring the uniform solution at room temperature for 6 hours at 200r/min to obtain AgMnCo-LDH; (6) After the reaction is finished, centrifuging the 5AgMnCo-LDH solution, wherein the centrifugation parameters are as follows: 8000 turns/min for 5min, washing for 5 times by deionized water, and finally performing forced air drying for 10h at the temperature of 80 ℃ to obtain a solid product 5AgMnCo-LDH (abbreviated as 5 AgMCL); (7) The above solid product is in H 2 Calcining at 150 ℃ for 2H under the atmosphere of a/Ar mixed gas, and representing the obtained sample as 5AgMnCoLDH-H2 (abbreviated as 5 AgMCL-H2).
Example 3
The preparation method of the silver-based manganese cobalt hydrotalcite catalyst for thermally catalyzing formaldehyde degradation provided by the embodiment comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O)、5.8206g Co(NO 3 ) 2 ·6H 2 O and 0.5036g AgNO 3 Adding the solution A into 30mL of deionized water, and marking as a solution A; (2) 0.8g of NaOH (1 mol/L) and 1.056g of Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 0.5g NH 4 Mixing the F and 1g of PVP to prepare a solution C; (4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH =10 of the solution; (5) Uniformly stirring the uniform solution at room temperature at 1000r/min for 6h to obtain AgMnCo-LDH; (6) After the reaction is finished, centrifuging the 5AgMnCo-LDH solution, wherein the centrifugation parameters are as follows: 8000 turns/min for 5min, washing for 4 times by deionized water, and finally blowing and drying for 8h at 80 ℃ to obtain a solid product 8AgMnCo-LDH (abbreviated as 8 AgMCL); (7) The above solid product is in H 2 Calcining at 150 ℃ for 2H under the atmosphere of an/Ar mixed gas, and expressing the obtained sample as 8AgMnCoLDH-H2 (abbreviated as 8 AgMCL-H2);
example 4
The preparation method of the silver-based manganese cobalt hydrotalcite catalyst for thermal catalysis of formaldehyde degradation provided by the embodiment comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O)、5.8206g Co(NO 3 ) 2 ·6H 2 O and 0.5036g AgNO 3 Adding the solution A into 30mL of deionized water, and marking as a solution A; (2) 0.8g of NaOH (1 mol/L) and 1.056g of Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 1g of NH 4 Mixing the F and 1.5g of PVP to prepare solution C; (4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH of the solution =10; (5) Uniformly stirring the uniform solution at room temperature for 6 hours at 1000r/min to obtain AgMnCo-LDH; (6) After the reaction is completed, centrifuging the 5AgMnCo-LDH solution, wherein the centrifugation parameters are as follows: 8000 revolutions/min for 5min, washing for 4 times by deionized water, and finally blowing and drying for 8h at 80 ℃ to obtain a solid product 8AgMnCo-LDH (abbreviated as 8 AgMCL); (7) The above solid product is in H 2 Calcining at 150 ℃ for 4H under the atmosphere of an/Ar mixed gas, and expressing the obtained sample as 8AgMnCo-LDH-H4 (abbreviated as 8 AgMCL-H4);
example 5
The preparation method of the silver-based manganese cobalt hydrotalcite catalyst for thermal catalysis of formaldehyde degradation provided by the embodiment comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O)、5.8206g Co(NO 3 ) 2 ·6H 2 O and 0.5036g AgNO 3 Adding the solution into 30mL of deionized water, and marking as a solution A; (2) 0.8g NaOH (1 mol/L) and 1.056g Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 1g of NH 4 Mixing the F and 1.5g of PVP to prepare a solution C; (4) Simultaneously dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C to obtain a mixtureA solution, dropwise adding NaOH solution in the dropwise adding process to maintain the pH =10; (5) Uniformly stirring the uniform solution at room temperature for 6 hours at 8000r/min to obtain 8AgMnCo-LDH; (6) After the reaction is finished, centrifuging the 5AgMnCo-LDH solution, wherein the centrifugation parameters are as follows: 8000 revolutions/min for 5min, washing for 3 times by deionized water, and finally blowing and drying for 8h at 80 ℃ to obtain a solid product 8AgMnCo-LDH (abbreviated as 8 AgMCL); (7) The solid product is in H 2 Calcining at 150 ℃ for 6H under the atmosphere of an/Ar mixed gas, and expressing the obtained sample as 8AgMnCoLDH-H6 (abbreviated as 8 AgMCL-H6);
example 6
The preparation method of the silver-based manganese cobalt hydrotalcite catalyst for thermal catalysis of formaldehyde degradation provided by the embodiment comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O)、5.8206g Co(NO 3 ) 2 ·6H 2 O and 0.3148g AgNO 3 Adding the solution into 30mL of deionized water, and marking as a solution A; (2) 0.8g NaOH (1 mol/L) and 1.056g Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 1g of NH 4 Mixing the F and 1.5g of PVP to prepare solution C; (4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH =10 of the solution; (5) Uniformly stirring the uniform solution at room temperature at 10000r/min for 6h to obtain 5AgMnCo-LDH; (6) After the reaction is completed, centrifuging the 5AgMnCo-LDH solution, wherein the centrifugation parameters are as follows: 8000 turns/min for 5min, washing for 3-5 times by deionized water, and finally performing forced air drying for 8h at 80 ℃ to obtain a solid product 5AgMnCo-LDH (abbreviated as 5 AgMCL); (7) The solid product is in H 2 Calcining at 150 ℃ for 6H under the atmosphere of an/Ar mixed gas, and expressing the obtained sample as 5AgMnCoLDH-H6 (abbreviated as 5 AgMCL-H6);
comparative example 1
A preparation method of a silver-based manganese cobalt hydrotalcite catalyst for thermal catalysis of formaldehyde degradation comprises the following specific steps:
(1) 2.386mL of Mn (NO) 3 ) 2 Solution (50 wt.% in H) 2 O) and 5.8206g Co (NO) 3 ) 2 ·6H 2 O was added to 30mL of deionisedIn water, marking as solution A; (2) 0.8g NaOH (1 mol/L) and 1.056g Na were taken 2 CO 3 Adding the mixed solution into 30mL of deionized water, and marking as a mixed alkali solution B; (3) Take 1g of NH 4 Mixing the F and 1.5g of PVP to prepare solution C; (4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH =10 of the solution; (5) Uniformly stirring the uniform solution at room temperature for 6 hours to obtain MnCoLDH nanosheets; (6) After the reaction is finished, centrifuging the solution, washing the solution by deionized water, and finally performing forced air drying to obtain a solid product MnCo-LDH (abbreviated as MCL); (7) 1g of MnCoLDH was added to 30mL of deionized water, and 0.5036g of AgNO was added 3 And then uniformly stirring for 24h, centrifuging the solution, washing with deionized water, and finally performing forced air drying to obtain a solid product 8AgMnCoLDH-S (abbreviated as 8 AgMCL-S). (8) The solid product is in H 2 the/Ar mixed atmosphere is calcined for 6H at 150 ℃, and the obtained sample is expressed as 8AgMnCoLDH-S-H (abbreviated as 8 AgMCL-S-H).
TABLE 1 Activity evaluation results of Ag/LDH catalysts
Examples 1-6 prepare Ag/LDH-H using a one-step process, while the comparative example prepares Ag/LDH-H-S by a classical impregnation process. As can be seen from the table, although the Ag content of the comparative example exceeds that of the examples, the catalyst has no higher conversion rate of catalytic formaldehyde than the examples under the same conditions; this shows that the Ag/LDH prepared by one-step method has good formaldehyde catalytic activity. In addition, the noble metal Ag content still can obtain good catalytic activity at 8 wt.%. Thus, examples 1-6 provide a thermal catalyst with excellent activity.
The above are only preferred embodiments of the present invention, and it should be noted that it is obvious to those skilled in the art that various changes and modifications can be made without departing from the structure of the present invention, which will not affect the effect of the implementation of the present invention and the practicability of the patent.
Claims (9)
1. The preparation method of the silver-doped manganese-cobalt hydrotalcite catalyst is characterized by sequentially comprising the following steps of:
(1) Preparing a mixed solution A of manganese nitrate, cobalt nitrate and silver nitrate;
(2) Preparing NaOH and NaCO 3 The mixed alkali solution B of (1);
(3) Reacting NH 4 Mixing the F and PVP to prepare solution C;
(4) Dropwise adding the solution A in the step (1) and the solution B in the step (2) into the solution C simultaneously to obtain a uniform solution, and dropwise adding a NaOH solution in the dropwise adding process to maintain the pH =10 of the solution;
(5) Uniformly stirring the uniform solution at 50-80 ℃ for 5-8h to obtain an AgMnCo-LDH nanosheet solution;
(6) After the reaction is finished, centrifuging the AgMnCo-LDH nanosheet solution, washing with deionized water, and finally performing forced air drying to obtain a solid product AgMnCo-LDH;
(7) The above solid product contains 5% of H 2 H of (A) to (B) 2 The mixture/Ar is further calcined, and the obtained sample is expressed as AgMnCoLDH-H.
2. The method for preparing the silver-doped manganese cobalt hydrotalcite catalyst according to claim 1, wherein the molar ratio of the manganese nitrate, the cobalt nitrate and the silver nitrate in step (1) is 1: 1.0-3.0: 0.01-0.1.
3. The method for preparing silver doped manganese cobalt hydrotalcite catalyst according to claim 1, wherein NaOH and NaCO are used in step (2) 3 The molar ratio of (A) to (B) is 0.5-1.0: 1.
4. The method for preparing the silver doped manganese cobalt hydrotalcite catalyst according to claim 1, wherein the NaOH concentration in step (4) is 1mol/L.
5. The method for preparing the silver-doped manganese cobalt hydrotalcite catalyst according to claim 1, wherein the stirring speed in the step (5) is 200-2000r/min.
6. The method for preparing the silver-doped manganese cobalt hydrotalcite catalyst according to claim 1, wherein the centrifugation parameters in step (6) are as follows: 8000 rpm for 5min; the washing conditions were: washing with deionized water for 3-5 times; the drying temperature is 80 ℃ and the drying time is 6-10 h.
7. The method for preparing the silver-doped manganese cobalt hydrotalcite catalyst according to claim 1, wherein the calcination temperature in step (7) is 100-300 ℃ and the calcination time is 2-6h.
8. A silver doped manganese cobalt hydrotalcite catalyst, characterized in that it is prepared by the process according to any of claims 1 to 7.
9. The method for catalytically degrading formaldehyde by using the silver-doped manganese cobalt hydrotalcite catalyst as claimed in claim 8, wherein the catalytic conditions are as follows: the concentration of formaldehyde is-35 ppm, the space velocity is 22200 mL/(g.h), and the reaction temperature is 30 ℃.
The AgMnCo-LDH catalyst provided by the invention is applied to the field of normal-temperature thermal catalysis. The catalyst has certain catalytic efficiency on monomer micromolecular organic matters, and can be used for degrading common organic pollutants in the air.
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