CN111013602A - Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof - Google Patents

Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof Download PDF

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CN111013602A
CN111013602A CN201911326004.8A CN201911326004A CN111013602A CN 111013602 A CN111013602 A CN 111013602A CN 201911326004 A CN201911326004 A CN 201911326004A CN 111013602 A CN111013602 A CN 111013602A
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CN111013602B (en
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夏启斌
付鹏
陈嘉宇
陈洋
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Guangzhou Huanyuan Technology Co ltd
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Abstract

The invention belongs to the field of indoor formaldehyde catalytic oxidation, and discloses a formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature, and a preparation method and application thereof. The preparation method of the formed Mn/Co-based catalyst comprises the following steps: dissolving a polymer and cobalt salt by using an organic solvent, adding an organic ligand, and uniformly stirring to obtain a mixed solution; adding the manganese salt solution into the mixed solution, stirring at normal temperature for reaction, and filtering to obtain a catalyst precursor; and drying and calcining the catalyst precursor, adding a binder into the catalyst precursor, carrying out extrusion forming, and drying and calcining the mixture to obtain the target catalyst. The method has the advantages of easily-accessible and cheap raw materials, simple preparation process, and high cost of noble metal catalystThe molded Mn/Co based catalyst is used for 15000h‑1Can realize the complete catalytic oxidation of formaldehyde at high airspeed, and solves the problems that the catalytic activity of the prior non-noble metal catalyst is low and the catalytic activity is reduced at high airspeed.

Description

Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof
Technical Field
The invention belongs to the field of indoor formaldehyde catalytic oxidation, and particularly relates to a formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature, and a preparation method and application thereof.
Background
As an economic chemical, formaldehyde is widely applied to the market, indoor articles including furniture, wood floors and various plastic products contain a certain amount of formaldehyde, the formaldehyde slowly volatilizes over time, and the human body contacts with the formaldehyde at a concentration of more than 0.08mg/m for a long time3The formaldehyde can cause sensory disturbance and immunity reduction, and even can cause diseases such as leukemia, mental depression and the like. Therefore, the development of a formaldehyde purification technology with high formaldehyde purification efficiency, low operation cost and high feasibility has profound practical significance.
Among formaldehyde pollution control methods, the catalytic oxidation method, which is a method of oxidizing formaldehyde into nontoxic CO using oxygen in the air as an oxidant through a catalyst, has been widely studied because of its advantages of no secondary pollution, low energy consumption, high degradation efficiency, and the like2And H2And O. At present, the research on formaldehyde catalysts represented by noble metals such as Ag and Pt is mature, and the complete removal of formaldehyde can be realized at room temperature. Guo 2913578, et al, in chinese patent authorization document CN106964348B, disclose a room temperature formaldehyde removal catalyst supporting platinum or palladium on AlOOH. When the initial concentration of formaldehyde is 80ppm, the total flow of gas is 300ml/min, and the space velocity is 180000h-1The catalyst can maintain the formaldehyde conversion rate close to 100 percent within 150 hours. However, the noble metal catalyst is expensive, and is not suitable for the removal of formaldehyde in the room by industrial mass production. Therefore, the non-noble metal catalyst with lower cost becomes a research hotspot in the field of formaldehyde catalysis at present. At present, researchers have conducted a great deal of research on non-noble metal catalysts, such as single metal oxides or multi-metal composite oxides of Mn, Co, and the like. Lusu Red et al, in Chinese patent publication CN105268452A, disclose a Chinese medicineMesoporous SiO2The formaldehyde degradation catalyst loaded with the copper-manganese composite oxide has the advantages of simple preparation process and lower cost, and is beneficial to industrial popularization. But the catalyst can degrade formaldehyde completely at 75-125 ℃, and can not meet the requirement of completely converting formaldehyde indoors.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a preparation method of a formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature. The method has the advantages of simple preparation method, low energy consumption, low price, high-efficiency catalytic oxidation of low-concentration formaldehyde at high airspeed and the like.
Another object of the present invention is to provide a shaped Mn/Co based catalyst capable of decomposing formaldehyde at room temperature prepared by the above method.
Still another object of the present invention is to provide the use of the above shaped Mn/Co based catalyst capable of decomposing formaldehyde at room temperature.
The purpose of the invention is realized by the following scheme:
a preparation method of a formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature comprises the following steps:
(1) dissolving a polymer and cobalt salt by using an organic solvent, adding an organic ligand, and uniformly stirring to obtain a mixed solution;
(2) adding a manganese salt solution into the mixed solution obtained in the step (1) under the stirring condition, then stirring at normal temperature for reaction, and filtering to obtain a catalyst precursor;
(3) drying and calcining the catalyst precursor to obtain Mn/Co-based catalyst powder;
(4) and adding a binder into the prepared Mn/Co catalyst powder, performing extrusion forming, drying and calcining to obtain the formed Mn/Co-based catalyst.
The polymer in the step (1) is at least one of polyvinylpyrrolidone (PVP), Polyacrylonitrile (PAN) and Polyethylene (PE), and is preferably polyvinylpyrrolidone (PVP).
The organic ligand in the step (1) is at least one of formic acid, oxalic acid, 2, 5-dihydroxy terephthalic acid and terephthalic acid, and formic acid is preferred.
The cobalt salt in the step (1) is Co (NO)3)2·6H2O、Co(CH3COO)2·4H2O and CoSO4·7H2At least one of O, preferably Co (NO)3)2·6H2O；
The polymer, the cobalt salt and the organic ligand in the step (1) are used in the following amounts: the ratio of the mass of the polymer to the molar amount of the cobalt salt is 15g:1mmol to 3g:2mmol, preferably 15g:8 mmol; the molar ratio of the cobalt salt to the organic ligand is 1: 1-1: 10, preferably 1: 5.
The organic solvent in the step (1) is a mixed solution of N, N-dimethylformamide and ethanol, and the volume ratio is 5: 1-1: 5, preferably 1: 1.
The manganese salt in the step (2) is Mn (NO)3)2、MnSO4And Mn (CH)3COO)2Is preferably Mn (NO)3)2(ii) a The manganese salt solution in the step (2) is a manganese salt aqueous solution with the concentration of 10-50 mmol/L, and preferably a manganese salt aqueous solution with the concentration of 20 mmol/L;
the dosage of the manganese salt solution in the step (2) meets the following requirements: the molar ratio of the manganese element in the manganese salt solution to the cobalt element in the mixed solution obtained in the step (1) is 5: 1-1: 5, and preferably 1: 4.
The manganese salt solution in the step (2) is preferably dripped in a dripping mode, and the dripping speed is 0.5-3 mL/min, preferably 1 mL/min;
the normal-temperature stirring reaction in the step (2) is carried out for 0.5-3 h, preferably for 2 h.
The drying temperature in the step (3) is 80-120 ℃, and preferably 100 ℃; the drying time is 6-12 h, preferably 8 h; the calcination in the step (3) is carried out in a nitrogen atmosphere, and the calcination temperature is 200-400 ℃, preferably 300 ℃; the calcination time is 1-4 h, preferably 2 h.
The binder in the step (4) is at least one of bentonite, kaolin, clay and sesbania powder, preferably kaolin; the using amount of the binder is such that the mass of the binder accounts for 2-15%, preferably 10% of the total mass of the Mn/Co catalyst powder and the binder.
The drying temperature in the step (4) is 60-120 ℃, and preferably 100 ℃; the drying time is 6-14 h, preferably 12 h. The calcination in the step (4) is carried out in an air atmosphere, and the calcination temperature is 300-500 ℃, preferably 400 ℃; the calcination time is 1-4 h, preferably 2 h.
The formed Mn/Co-based catalyst which can decompose formaldehyde at room temperature and is prepared by the method.
The formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature is applied to the field of treating indoor formaldehyde pollution.
The mechanism of the invention is as follows:
the invention provides a formed Mn/Co-based catalyst for decomposing formaldehyde at room temperature, which is characterized in that a catalyst precursor can be obtained by adding reactants under the action of a polymer and stirring for 0.5-3 h at normal temperature, so that the time and energy consumption for synthesizing the catalyst precursor are greatly reduced, and then the formed Mn/Co-based catalyst is prepared by activation and forming. The raw materials of the formed Mn/Co-based catalyst are cheap and easy to obtain, the preparation process is simple, the defect that the noble metal catalyst is expensive is overcome, and meanwhile, the formed Mn/Co-based catalyst greatly improves the catalytic activity due to the advantages of regular pore channel structure, dispersed metal active sites and the like, and the catalytic activity is improved at 15000h-1Can also realize the complete catalytic oxidation of formaldehyde at high space velocity. Solves the problems of lower catalytic activity and reduced catalytic activity at high space velocity of the prior non-noble metal catalyst.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature, prepared by the method, has a regular pore channel structure, and Mn and Co active components are highly dispersed on the surface of the catalyst, so that the removal efficiency of formaldehyde at room temperature is greatly improved. Meanwhile, the pore structure of the Mn/Co-based catalyst is not damaged after molding, and compared with a powder catalyst, the Mn/Co-based catalyst has smaller resistance and larger purified air amount. The formed Mn/Co-based catalyst can still realize complete conversion under the conditions of low initial concentration of formaldehyde and high space velocity, and solves the problem of reduced catalytic activity under the conditions of low concentration of formaldehyde or high space velocity.
(2) The catalyst is a non-noble metal catalyst, has low production cost and very simple preparation process, and is beneficial to industrial expanded production.
(3) When the initial concentration of formaldehyde is 1-10 ppm, the total flow of gas is 200ml/min, and the space velocity is 150000h-1When the relative humidity is 50 percent, the decomposition rate of the formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature, which is prepared by the invention, on formaldehyde is kept above 98 percent and can reach 100 percent at most.
Drawings
FIG. 1 is a graph showing the formaldehyde removal effect of the formed Mn/Co-based catalysts Mn1Co 4-PVP-formic acid, Mn4Co 1-PE-formic acid, Mn4Co1-PVP-PTA and Mn1Co1-PE-PTA capable of decomposing formaldehyde at room temperature, prepared in examples 1-4;
FIG. 2 is a graph showing the results of a life test at room temperature for the Mn1Co 4-PVP-formic acid shaped Mn/Co based catalyst capable of decomposing formaldehyde at room temperature prepared in example 1 and the Mn/Co based catalyst powder prepared in step (3) of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) 1.5g of polyvinylpyrrolidone (PVP) and 0.8mmol of Co (NO)3)2·6H2Dissolving O in 40mL of mixed solution of N, N-dimethylformamide and 40mL of ethanol, adding 4mmol of formic acid, and uniformly stirring to obtain mixed solution;
(2) adding 0.2mmol of Mn (NO)3)2Dissolving 10mL of water, dropwise adding the solution into the mixed solution obtained in the step (1) at the speed of 1mL/min under the stirring condition, stirring at normal temperature for 2h, and filtering to obtain a catalyst precursor;
(3) drying the catalyst precursor in an oven at 100 ℃ for 8h, and calcining the catalyst precursor for 2h under the conditions of nitrogen atmosphere and 300 ℃ to obtain Mn/Co-based catalyst powder;
(4) and (3) adding 1g of kaolin into 9g of the prepared Mn/Co-based catalyst powder, carrying out extrusion forming, drying in an oven at 100 ℃ for 12h, and calcining at 400 ℃ for 2h to obtain the formed Mn/Co-based catalyst. (Note as Mn1Co 4-PVP-formic acid)
Example 2
(1) 1.5g of Polyethylene (PE) and 0.2mmol of Co (NO)3)2·6H2Dissolving O in 40mL of mixed solution of N, N-dimethylformamide and 40mL of ethanol, adding 1mmol of formic acid, and uniformly stirring to obtain mixed solution;
(2) adding 0.8mmol of Mn (NO)3)2Dissolving 30mL of water, dropwise adding the solution into the mixed solution obtained in the step (1) at the speed of 1mL/min under the stirring condition, stirring at normal temperature for 2h, and filtering to obtain a catalyst precursor;
(3) drying the catalyst precursor in an oven at 80 ℃ for 12h, and calcining the catalyst precursor for 2h at 300 ℃ in a nitrogen atmosphere to obtain Mn/Co-based catalyst powder;
(4) and (3) adding 1g of kaolin into 9g of the prepared Mn/Co-based catalyst powder, carrying out extrusion forming, drying in an oven at 100 ℃ for 12h, and calcining at 400 ℃ for 2h to obtain the formed Mn/Co-based catalyst. (as Mn4Co 1-PE-formic acid)
Example 3
(1) 1.8g of polyvinylpyrrolidone (PVP) and 0.2mmol of Co (NO)3)2·6H2Dissolving O in 40mL of mixed solution of N, N-dimethylformamide and 40mL of ethanol, adding 1mmol of terephthalic acid, and uniformly stirring to obtain mixed solution;
(2) adding 0.8mmol of Mn (NO)3)2Dissolving 30mL of water, dropwise adding the solution into the mixed solution obtained in the step (1) at the speed of 1.5mL/min under the stirring condition, stirring at normal temperature for 2h, and filtering to obtain a catalyst precursor;
(3) drying the catalyst precursor in an oven at 80 ℃ for 12h, and calcining the catalyst precursor for 2h at 300 ℃ in a nitrogen atmosphere to obtain Mn/Co-based catalyst powder;
(4) and (3) adding 1g of kaolin into 9g of the prepared Mn/Co-based catalyst powder, carrying out extrusion forming, drying in an oven at 100 ℃ for 12h, and calcining at 400 ℃ for 2h to obtain the formed Mn/Co-based catalyst. (as Mn4Co1-PVP-PTA)
Example 4
(1) 1.5g of Polyethylene (PE) and 0.8mmol of Co (NO)3)2·6H2Dissolving O in 40mL of mixed solution of N, N-dimethylformamide and 40mL of ethanol, adding 4mmol of terephthalic acid, and uniformly stirring to obtain mixed solution;
(2) adding 0.8mmol of Mn (NO)3)2Dissolving 30mL of water, dropwise adding the solution into the mixed solution obtained in the step (1) at the speed of 1.5mL/min under the stirring condition, stirring at normal temperature for 2h, and filtering to obtain a catalyst precursor;
(3) drying the catalyst precursor in an oven at 100 ℃ for 12h, and calcining the catalyst precursor for 2h under the conditions of nitrogen atmosphere and 300 ℃ to obtain Mn/Co-based catalyst powder;
(4) and (3) adding 1g of kaolin into 9g of the prepared Mn/Co-based catalyst powder, carrying out extrusion forming, drying in an oven at 100 ℃ for 12h, and calcining at 400 ℃ for 2h to obtain the formed Mn/Co-based catalyst. (as Mn1Co1-PE-PTA)
The application example is as follows: formaldehyde catalytic oxidation performance test
500mg of the molded Mn/Co-based catalyst in examples 1 to 4 and the Mn/Co-based catalyst powder in example 1 were respectively charged into a formaldehyde reaction apparatus to perform a formaldehyde catalytic oxidation performance test. The test conditions were as follows: the temperature of the reaction system is room temperature, the content of formaldehyde is 5ppm, the total flow of gas is 200mL/min, and the space velocity is 150000h-1The relative humidity was 30%. The formaldehyde concentration is detected by a PortaSens II gas detector, and the formaldehyde removal rate is calculated to evaluate the formaldehyde catalytic oxidation performance of the formed Mn/Co-based catalyst. Wherein, the formaldehyde removal rate is (formaldehyde inlet concentration-formaldehyde inlet concentration) ÷ formaldehyde inlet concentration × 100%.
FIG. 1 is a graph showing the formaldehyde removing effect of the formed Mn/Co based catalysts Mn1Co 4-PVP-formic acid, Mn4Co 1-PE-formic acid, Mn4Co1-PVP-PTA and Mn1Co1-PE-PTA which can decompose formaldehyde at room temperature prepared in examples 1-4 under the same conditions, and it can be seen from FIG. 1 that the formed Mn/Co based catalysts Mn1Co 4-PVP-formic acid in example 1 are compared with those in examples 2, 3 and example 3 under the same conditionsThe shaped Mn/Co based catalyst in example 4 showed more excellent formaldehyde removal performance at a space velocity of 150000h-1And then, the removal rate of formaldehyde is kept above 98% within 1-6 h, and can reach 100% at most.
FIG. 2 is a graph showing the results of a life test of the room temperature formaldehyde-decomposable Mn1Co 4-PVP-formic acid molded Mn/Co-based catalyst prepared in example 1 and the Mn/Co-based catalyst powder prepared in step (3) of example 1 at room temperature, and it can be seen from FIG. 2 that the removal rate (conversion rate) of formaldehyde from the Mn/Co-based catalyst powder gradually decreases with the lapse of time in the test time range of 300 hours. The Mn1Co 4-PVP-formic acid formed Mn/Co based catalyst has small fluctuation of a formaldehyde removal rate curve, the removal rate is always kept above 98 percent and can reach 100 percent at most, and excellent formaldehyde catalytic oxidation performance and stability are shown.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a formed Mn/Co-based catalyst for decomposing formaldehyde at room temperature is characterized by comprising the following steps:
(1) dissolving a polymer and cobalt salt by using an organic solvent, adding an organic ligand, and uniformly stirring to obtain a mixed solution;
(2) adding a manganese salt solution into the mixed solution obtained in the step (1) under the stirring condition, then stirring at normal temperature for reaction, and filtering to obtain a catalyst precursor;
(3) drying and calcining the catalyst precursor to obtain Mn/Co-based catalyst powder;
(4) and adding a binder into the prepared Mn/Co catalyst powder, performing extrusion forming, drying and calcining to obtain the formed Mn/Co-based catalyst.
2. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
the polymer in the step (1) is at least one of polyvinylpyrrolidone, polyacrylonitrile and polyethylene;
the organic ligand in the step (1) is at least one of formic acid, oxalic acid, 2, 5-dihydroxy terephthalic acid and terephthalic acid.
3. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
the cobalt salt in the step (1) is Co (NO)3)2·6H2O、Co(CH3COO)2·4H2O and CoSO4·7H2At least one of O;
the manganese salt in the step (2) is Mn (NO)3)2、MnSO4And Mn (CH)3COO)2At least one of;
the organic solvent in the step (1) is a mixed solution of N, N-dimethylformamide and ethanol, and the volume ratio is 5: 1-1: 5.
4. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
the polymer, the cobalt salt and the organic ligand in the step (1) are used in the following amounts: the ratio between the mass of polymer and the molar amount of cobalt salt was 15g:1 mmol-3 g:2mmol of the active carbon; the molar ratio of the cobalt salt to the organic ligand is 1: 1-1: 10;
the dosage of the manganese salt solution in the step (2) meets the following requirements: the molar ratio of the manganese element in the manganese salt solution to the cobalt element in the mixed solution obtained in the step (1) is 5: 1-1: 5.
5. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
adding the manganese salt solution in the step (2) in a dropwise manner at a speed of 0.5-3 mL/min;
and (3) stirring and reacting at normal temperature in the step (2) for 0.5-3 h.
6. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
the drying temperature in the step (3) is 80-120 ℃, and the drying time is 6-12 h;
and (4) calcining in the step (3) in a nitrogen atmosphere at the temperature of 200-400 ℃ for 1-4 h.
7. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
the binder in the step (4) is at least one of bentonite, kaolin, clay and sesbania powder; the using amount of the binder meets the requirement that the mass of the binder accounts for 2-15% of the total mass of the Mn/Co catalyst powder and the binder.
8. The method of preparing a shaped Mn/Co-based catalyst for room temperature decomposition of formaldehyde according to claim 1, wherein:
the drying temperature in the step (4) is 60-120 ℃; the drying time is 6-14 h;
and (4) calcining in an air atmosphere at the temperature of 300-500 ℃ for 1-4 h.
9. A shaped Mn/Co based catalyst for decomposing formaldehyde at room temperature prepared by the method of any one of claims 1 to 8.
10. The use of the shaped Mn/Co based catalyst for room temperature decomposition of formaldehyde according to claim 9 in the field of remediation of indoor formaldehyde pollution.
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CN113908628A (en) * 2021-09-29 2022-01-11 华东师范大学重庆研究院 Cobalt-based oxide superfine glass fiber gas phase purification filter screen and preparation method thereof
CN114425365A (en) * 2022-01-29 2022-05-03 重庆交通大学 Preparation method of defect-rich Mn-Co metal oxide catalyst
CN114797888A (en) * 2022-03-14 2022-07-29 杭州妙蓝环保科技有限公司 Air purifying agent for removing formaldehyde indoors and preparation method thereof
CN115487826A (en) * 2022-09-26 2022-12-20 江苏中江材料技术研究院有限公司 Silver-doped manganese-cobalt hydrotalcite catalyst, preparation method thereof and method for degrading formaldehyde
CN115785037A (en) * 2022-11-28 2023-03-14 安徽工业大学 Green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing tandem oxidation of 5-hydroxymethylfurfural

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102962036A (en) * 2012-10-30 2013-03-13 中国科学院大连化学物理研究所 Porous metal organic framework material based on transition metal cobalt and preparation method thereof
CN104338528A (en) * 2013-07-30 2015-02-11 江苏瑞丰科技实业有限公司 Preparation of room temperature formaldehyde catalyst
WO2016171807A1 (en) * 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Catalyst composition comprising fluorided support and processes for use thereof
CN107020387A (en) * 2016-02-01 2017-08-08 北京化工大学 A kind of method that normal temperature and pressure quickly prepares copper nano-wire-metal organic framework ZIF-8 composites
CN107362807A (en) * 2017-07-31 2017-11-21 华南理工大学 A kind of Mn/Co bases low temperature SCO catalyst and preparation method thereof
CN107497495A (en) * 2017-10-12 2017-12-22 天津工业大学 A kind of preparation method of hud typed metal organic framework heterogeneous material compound
CN108671937A (en) * 2018-05-16 2018-10-19 华侨大学 A kind of preparation method and applications of copper-manganese composite oxide catalysts
CN108906034A (en) * 2018-06-27 2018-11-30 宁波智通环保科技有限公司 A kind of catalysis material and preparation method thereof of room-temperature decomposition formaldehyde
CN109351361A (en) * 2018-10-12 2019-02-19 深圳大学 A kind of bifunctional catalyst and preparation method
CN109400905A (en) * 2018-11-26 2019-03-01 重庆文理学院 A kind of metal organic framework Mn-BTC and preparation method and application
CN109876776A (en) * 2019-02-02 2019-06-14 北京建筑大学 Indium base MOF micro-nano powder and its room temperature preparation method and application
CN109926084A (en) * 2019-04-04 2019-06-25 西安交通大学 One kind is based on hydrogen reduction/analysis oxygen double-function catalyzing material and preparation method derived from more metal MOFs
CN110433854A (en) * 2019-07-16 2019-11-12 华南理工大学 A kind of composite catalyst and the preparation method and application thereof of room temperature degradation of formaldehyde

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102962036A (en) * 2012-10-30 2013-03-13 中国科学院大连化学物理研究所 Porous metal organic framework material based on transition metal cobalt and preparation method thereof
CN104338528A (en) * 2013-07-30 2015-02-11 江苏瑞丰科技实业有限公司 Preparation of room temperature formaldehyde catalyst
WO2016171807A1 (en) * 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Catalyst composition comprising fluorided support and processes for use thereof
CN107020387A (en) * 2016-02-01 2017-08-08 北京化工大学 A kind of method that normal temperature and pressure quickly prepares copper nano-wire-metal organic framework ZIF-8 composites
CN107362807A (en) * 2017-07-31 2017-11-21 华南理工大学 A kind of Mn/Co bases low temperature SCO catalyst and preparation method thereof
CN107497495A (en) * 2017-10-12 2017-12-22 天津工业大学 A kind of preparation method of hud typed metal organic framework heterogeneous material compound
CN108671937A (en) * 2018-05-16 2018-10-19 华侨大学 A kind of preparation method and applications of copper-manganese composite oxide catalysts
CN108906034A (en) * 2018-06-27 2018-11-30 宁波智通环保科技有限公司 A kind of catalysis material and preparation method thereof of room-temperature decomposition formaldehyde
CN109351361A (en) * 2018-10-12 2019-02-19 深圳大学 A kind of bifunctional catalyst and preparation method
CN109400905A (en) * 2018-11-26 2019-03-01 重庆文理学院 A kind of metal organic framework Mn-BTC and preparation method and application
CN109876776A (en) * 2019-02-02 2019-06-14 北京建筑大学 Indium base MOF micro-nano powder and its room temperature preparation method and application
CN109926084A (en) * 2019-04-04 2019-06-25 西安交通大学 One kind is based on hydrogen reduction/analysis oxygen double-function catalyzing material and preparation method derived from more metal MOFs
CN110433854A (en) * 2019-07-16 2019-11-12 华南理工大学 A kind of composite catalyst and the preparation method and application thereof of room temperature degradation of formaldehyde

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XI WANG ET.AL: "MOF-derived metal oxide composite Mn2Co1Ox/CN for efficient formaldehyde oxidation at low temperature", 《CATAL. SCI. TECHNOL》 *
徐浩;张静;张古承;叶倩;周冠宇;杨富花;: "钴锰双金属氧化物催化过硫酸氢钾降解酸性橙7的研究" *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112191255A (en) * 2020-10-28 2021-01-08 南京融众环境工程研究院有限公司 Aluminum hydroxide and kaolin supported Cr-Cu-Mn-O mixed/composite oxide catalyst and application thereof
CN112191255B (en) * 2020-10-28 2023-05-05 南京融众环境工程研究院有限公司 Cr-Cu-Mn-O mixed/composite oxide catalyst supported by aluminum hydroxide and kaolin and application thereof
CN113908628A (en) * 2021-09-29 2022-01-11 华东师范大学重庆研究院 Cobalt-based oxide superfine glass fiber gas phase purification filter screen and preparation method thereof
CN114425365A (en) * 2022-01-29 2022-05-03 重庆交通大学 Preparation method of defect-rich Mn-Co metal oxide catalyst
CN114425365B (en) * 2022-01-29 2024-04-26 重庆交通大学 Preparation method of defect-rich Mn-Co metal oxide catalyst
CN114797888A (en) * 2022-03-14 2022-07-29 杭州妙蓝环保科技有限公司 Air purifying agent for removing formaldehyde indoors and preparation method thereof
CN114797888B (en) * 2022-03-14 2023-07-28 杭州妙蓝环保科技有限公司 Indoor formaldehyde-removing air purifying agent and preparation method thereof
CN115487826A (en) * 2022-09-26 2022-12-20 江苏中江材料技术研究院有限公司 Silver-doped manganese-cobalt hydrotalcite catalyst, preparation method thereof and method for degrading formaldehyde
CN115785037A (en) * 2022-11-28 2023-03-14 安徽工业大学 Green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing tandem oxidation of 5-hydroxymethylfurfural
CN115785037B (en) * 2022-11-28 2024-03-29 安徽工业大学 Green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing serial oxidation of 5-hydroxymethylfurfural

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