CN114950408B - ZnMn of controllably synthesized exposed crystal face 2 O 4 Method for preparing catalyst and ZnMn 2 O 4 Catalyst and its use - Google Patents

ZnMn of controllably synthesized exposed crystal face 2 O 4 Method for preparing catalyst and ZnMn 2 O 4 Catalyst and its use Download PDF

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CN114950408B
CN114950408B CN202210440632.4A CN202210440632A CN114950408B CN 114950408 B CN114950408 B CN 114950408B CN 202210440632 A CN202210440632 A CN 202210440632A CN 114950408 B CN114950408 B CN 114950408B
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znmn
catalyst
crystal face
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precursor
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CN114950408A (en
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张高科
程强
李源
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Wuhan University of Technology WUT
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Abstract

The invention relates to a ZnMn with controllable synthesis of an exposed crystal face 2 O 4 Catalyst process and ZnMn 2 O 4 The catalyst and the application thereof comprise the following steps: s100 is Mn (CH) 3 COO) 2 ·4H 2 O and Zn (CH) 3 COO) 2 ·2H 2 O is taken as a raw material, oxalic acid, ethanol and N-N dimethylformamide solution are added, and ZnMn is obtained through solvothermal reaction 2 O 4 A precursor; s200, znMn 2 O 4 The precursor is subjected to the conditions of 600 ℃ and air to obtain ZnMn with exposed {010} crystal face 2 O 4 A catalyst. The beneficial effects of the invention are as follows: the invention utilizes spinel structure compound ZnMn 2 O 4 Good light absorption capacity and photo-thermal conversion capacity, and can expose a large number of catalyst active sites by regulating and controlling proper crystal faces, and the ZnMn of the {010} crystal faces is exposed by adopting a preparation process combining a solvothermal method and a calcination method 2 O 4 A catalyst which achieves efficient conversion of toluene contaminants at lower ambient temperatures (156 ℃); the preparation process combining the solvothermal method and the calcination method has the advantages of simple operation, safety, low cost and the like, and ZnMn 2 O 4 The catalyst has wide sources of raw materials and is easy to obtain.

Description

ZnMn of controllably synthesized exposed crystal face 2 O 4 Method for preparing catalyst and ZnMn 2 O 4 Catalyst and its use
Technical Field
The invention relates to the technical field of nano material preparation and photo-thermal catalysis, in particular to ZnMn of a controllable synthesis exposed crystal face 2 O 4 Method for preparing catalyst and ZnMn 2 O 4 A catalyst and its use.
Background
The continuous development of the modern industry gradually increases the emission of Volatile Organic Compounds (VOCs), which causes serious harm to the natural environment and human health. Therefore, the research on the catalytic oxidation technology of VOCs is increasingly focused by researchers. In the prior art, the thermal catalytic oxidation technique is considered to be one of the effective techniques for removing VOCs. Although the thermal catalytic oxidation technology can effectively degrade VOCs in a mode of increasing the ambient temperature by externally heating and inputting energy, the process has high energy consumption and high cost, and is unfavorable for green development and application of the technology. Compared with the thermal catalysis technology, the photo-thermal catalysis technology can effectively utilize near infrared light and mid infrared light which occupy most of energy in a solar spectrum besides ultraviolet light and visible light in the solar light. The catalyst can effectively mineralize VOCs by absorbing photons to convert the photons into heat energy. In addition, the good light absorption capacity and light-heat conversion capacity of the catalyst surface in the photo-thermal catalysis process enable the local temperature of the catalyst surface to be rapidly increased in a short time. The process is favorable for the quick and efficient reaction of the VOCs on the surface of the catalyst, and can reduce the ambient temperature of the photo-thermal catalytic process, thereby greatly reducing the external energy required by the catalytic oxidation of the VOCs.
Based on the above discussion, if a material which can realize high-efficiency photo-thermal absorption and photo-thermal conversion efficiency and has photo-thermal catalytic activity can be explored, the development of a green, energy-saving and environment-friendly technology for effectively removing VOCs at low temperature without additional heat energy input can be expected.
Disclosure of Invention
The invention aims to provide a method for controllably synthesizing ZnMn with different exposed crystal faces 2 O 4 Method for preparing catalyst and application thereof to overcome the prior artThe operation is not enough.
The technical scheme for solving the technical problems is as follows:
ZnMn of controllably synthesized exposed crystal face 2 O 4 A method of catalyst comprising the steps of:
s100 is Mn (CH) 3 COO) 2 ·4H 2 O and Zn (CH) 3 COO) 2 ·2H 2 O is taken as a raw material, oxalic acid, ethanol and N-N dimethylformamide solution are added, and ZnMn is obtained through solvothermal reaction 2 O 4 A precursor;
s200, znMn 2 O 4 The precursor is subjected to the conditions of 600 ℃ and air to obtain ZnMn with exposed {010} crystal face 2 O 4 A catalyst.
The beneficial effects of the invention are as follows: the invention utilizes spinel structure compound ZnMn 2 O 4 Good light absorption capacity and photo-thermal conversion capacity, and can expose a large number of catalyst active sites by regulating and controlling proper crystal faces, and the ZnMn of the {010} crystal faces is exposed by adopting a preparation process combining a solvothermal method and a calcination method 2 O 4 A catalyst which achieves efficient conversion of toluene contaminants at lower ambient temperatures (156 ℃); the preparation process combining the solvothermal method and the calcination method has the advantages of simple operation, safety, low cost and the like, and ZnMn 2 O 4 The catalyst has wide sources of raw materials and is easy to obtain.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the reaction temperature of the solvothermal reaction is 140-200 ℃ and the reaction time is 5-20h.
Further, the volume ratio of the ethanol to the N-N dimethylformamide is 3:2, and the oxalic acid content is 1-2g.
Further, S200 is specifically: znMn is added into 2 O 4 The precursor is placed in a muffle furnace, heated for a certain time, cooled to room temperature after finishing, and ZnMn with {010} crystal face exposed is obtained 2 O 4 A catalyst.
Further, the temperature is raised and maintained for a certain time, specifically, the temperature raising rate is 2 ℃/min, the temperature is raised to 600 ℃, and the constant temperature calcination is carried out for 2-10h at 600 ℃.
The other technical scheme of the invention is as follows:
ZnMn with exposed crystal face 2 O 4 The catalyst is prepared by adopting any one of the further methods.
The other technical scheme of the invention is as follows:
ZnMn with exposed crystal face 2 O 4 The application of the catalyst adopts ZnMn prepared by any one of the further methods 2 O 4 And (3) carrying out photo-thermal catalytic oxidation on the toluene by using a catalyst.
Drawings
FIG. 1 shows a ZnMn of a controlled synthesis of exposed crystal faces according to the invention 2 O 4 A method step diagram of the catalyst;
FIG. 2 shows ZnMn of a controlled synthesis of exposed crystal face according to the invention 2 O 4 Method for preparing catalyst and ZnMn 2 O 4 XRD spectra of ZMO-A, ZMO-B, ZMO-C prepared by the catalyst and the application specific examples 1-3 respectively;
FIG. 3 shows a ZnMn of a controlled synthesis of exposed crystal faces according to the invention 2 O 4 Method for photo-thermal catalyst and ZnMn 2 O 4 SEM spectrogram of ZMO-A prepared in specific example 1 of catalyst and application thereof;
FIG. 4 shows a ZnMn of a controlled synthesis of exposed crystal faces according to the invention 2 O 4 Method for photo-thermal catalyst and ZnMn 2 O 4 HRTEM spectrA of the catalyst and ZMO-A prepared in application specific example 1;
FIGS. 5-6 illustrate ZnMn of a controlled synthesis of exposed crystal faces according to the invention 2 O 4 Method for photo-thermal catalyst and ZnMn 2 O 4 SEM spectrograms of ZMO-B and ZMO-C respectively prepared from the catalyst and application specific examples 2-3;
FIG. 7 shows a ZnMn of a controlled synthesis of exposed crystal faces according to the invention 2 O 4 Method for photo-thermal catalyst and ZnMn 2 O 4 Catalyst and ZMO-A, CM prepared by the same in examples 1-3Effect of photo-thermal catalytic oxidation of toluene by O-B, CMO-C.
Detailed Description
Example 1 of the invention ZnMn of the controlled Synthesis of exposed Crystal face 2 O 4 A method of catalyst comprising the steps of:
s100 is Mn (CH) 3 COO) 2 ·4H 2 O and Zn (CH) 3 COO) 2 ·2H 2 O is taken as a raw material, oxalic acid, ethanol and N-N dimethylformamide solution are added, and ZnMn is obtained through solvothermal reaction 2 O 4 A precursor;
s200, znMn 2 O 4 The precursor is subjected to the conditions of 600 ℃ and air to obtain ZnMn with exposed {010} crystal face 2 O 4 A catalyst.
Example 2 of the invention ZnMn of the controlled Synthesis of exposed Crystal face 2 O 4 The method of the catalyst is based on the embodiment 1, the reaction temperature of the solvothermal reaction is 140-200 ℃ and the reaction time is 5-20h.
Example 3 of the invention ZnMn of the controlled Synthesis of exposed Crystal face 2 O 4 The catalyst was prepared according to the procedure of example 1, with a volume ratio of ethanol to N-N dimethylformamide of 3:2 and an oxalic acid content of 1-2g.
Example 4 of the invention ZnMn of the controlled Synthesis of exposed Crystal face 2 O 4 The method of the catalyst, based on example 1, S200 is specifically:
ZnMn is added into 2 O 4 The precursor is placed in a muffle furnace, heated for a certain time, cooled to room temperature after finishing, and ZnMn with {010} crystal face exposed is obtained 2 O 4 A catalyst.
Example 5 of the invention ZnMn of the controlled Synthesis of exposed Crystal face 2 O 4 The catalyst is prepared by heating to 600 deg.C for 2-10 hr based on the method of example 4, and calcining at 600 deg.C for 2-10 hr.
Example 6 ZnMn with exposed crystal face 2 O 4 Catalyst, from the method of any one of examples 1 to 5Is prepared by the method.
Example 7 of the present invention ZnMn with exposed crystal face 2 O 4 Use of a catalyst, znMn obtained by the method of any one of examples 1 to 5 2 O 4 Catalyst or ZnMn with example 6 with exposed crystal face 2 O 4 And (3) carrying out photo-thermal catalytic oxidation on the toluene by using a catalyst.
Example 1 controlled synthesis of ZnMn exposing {010} crystal face by the method of the present invention 2 O 4 A catalyst comprising the steps of: 2.45g of Mn (CH) 3 COO) 2 ·4H 2 O and 1.09g of Zn (CH) 3 COO) 2 ·2H 2 O is dissolved in 50ml of mixed solution of ethanol and N-N dimethylformamide, and the volume ratio of the ethanol to the N-N dimethylformamide is 3:2, stirring at room temperature to obtain a uniform solution; then adding 1.8g of oxalic acid into the solution, stirring, transferring into a polytetrafluoroethylene reaction kettle with the reaction volume of 90ml, putting into a drying box for solvothermal reaction at the reaction temperature of 170 ℃ to obtain ZnMn 2 O 4 A precursor; znMn is added into 2 O 4 Washing and drying the precursor, putting the precursor into a muffle furnace, heating to 600 ℃ for 2 hours, and cooling to room temperature after finishing to obtain ZnMn with exposed {010} crystal face 2 O 4 The catalyst (labeled ZMO-A).
XRD diffraction peak shape and position of ZMO-A sample in FIG. 2 and ZnMn 2 O 4 And the standard PDF cards correspond to each other one by one to indicate that the sample is successfully synthesized.
FIG. 3 is an SEM image of ZMO-A samples. ZnMn of the exposed crystal face of the graph surface 2 O 4 The shape of the catalyst is regular hexagonal nano-disk.
FIG. 4 is A HRTEM image of ZMO-A samples. ZnMn of the exposed crystal face of the graph surface 2 O 4 The nano-disk is composed of a plurality of hexagonal nano-sheets with the diameter of about 50 nm.
ZnMn of the {010} crystal face exposed synthesized in this example 2 O 4 Catalyst (ZMO-A) in the experiment of photo-thermal catalytic oxidation of toluene, the catalyst amount was 0.1g, the initial toluene concentration was 100ppm, and the illumination intensity was 500W/cm in A xenon lamp 2 Under the condition of reactionAfter 3 hours, the conversion rate of toluene reaches 93% (see FIG. 7), the final reaction environment temperature is 156 ℃, which shows that ZnMn of the exposed crystal face prepared by the method 2 O 4 The catalyst has good photo-thermal catalytic activity.
Example 2 controlled Synthesis of ZnMn exposing {11-1} crystal face 2 O 4 A method of catalyst comprising the steps of: 2.45g of Mn (CH) 3 COO) 2 ·4H 2 O and 1.09g of Zn (CH) 3 COO) 2 ·2H 2 O is dissolved in 50ml of mixed solution of ethanol and water, and the volume ratio of the ethanol to the water is 3:2, stirring at room temperature to obtain a uniform solution; then adding 0.3g of oxalic acid into the solution, stirring, transferring into a polytetrafluoroethylene reaction kettle with the reaction volume of 90ml, putting into a drying box for solvothermal reaction, and obtaining ZnMn at the reaction temperature of 170 DEG C 2 O 4 A precursor; znMn is added into 2 O 4 Washing and drying the precursor, putting the precursor into a muffle furnace, heating to 600 ℃ for 2 hours, and cooling to room temperature after finishing to obtain ZnMn with exposed {11-1} crystal face 2 O 4 The catalyst (labeled ZMO-B).
XRD diffraction peak shape and position of ZMO-B sample in FIG. 2 and ZnMn 2 O 4 And the standard PDF cards correspond to each other one by one to indicate that the sample is successfully synthesized.
FIG. 5 is an SEM image of ZMO-B samples. The surface of the graph exposes ZnMn of {11-1} crystal face 2 O 4 The shape of the catalyst is a nano rod shape.
ZnMn of the exposed {11-1} crystal face synthesized in this example 2 O 4 In the experiment of photo-thermal catalytic oxidation of toluene, the catalyst amount was 0.1g, the initial toluene concentration was 100ppm, and 500W/cm was irradiated with a xenon lamp 2 After 3h of reaction, the conversion rate of toluene reaches 56% (see FIG. 7), the final reaction environment temperature is 154 ℃, which shows that the ZnMn with the {11-1} crystal face exposed prepared by the method 2 O 4 The catalyst has better photo-thermal catalytic activity.
Example 3 controlled Synthesis of ZnMn with exposed {1-1-1} crystal face 2 O 4 A method of catalyst comprising the steps of: 2.45g of Mn (C)H 3 COO) 2 ·4H 2 O and 1.09g of Zn (CH) 3 COO) 2 ·2H 2 O is dissolved in 210ml of mixed solution of n-hexane and n-amyl alcohol, and the volume ratio of n-hexane to n-amyl alcohol is 20:1, stirring at room temperature to obtain a uniform solution; then adding 3.6g of hexadecyl trimethyl ammonium bromide into the solution, stirring, adding 10ml of ammonium bicarbonate solution (0.12 mol/ml), mixing and stirring for 5h to obtain ZnMn 2 O 4 A precursor; washing and drying the ZnMn2O4 precursor, putting the dried ZnMn2O4 precursor into a muffle furnace, heating to 600 ℃ for 2h, cooling to room temperature after finishing, and obtaining the ZnMn with exposed {1-1-1} crystal face 2 O 4 The catalyst (labeled ZMO-C).
XRD diffraction peak shapes and positions of ZMO-C samples in FIG. 2 correspond to ZnMn2O4 standard PDF cards one by one, indicating successful synthesis of the samples.
FIG. 6 is an SEM image of ZMO-C samples. The surface of the graph is exposed to ZnMn of {1-1-1} crystal face 2 O 4 The shape of the catalyst is nano cube shape.
ZnMn of the exposed {1-1-1} crystal face synthesized in this example 2 O 4 In the experiment of photo-thermal catalytic oxidation of toluene, the catalyst amount was 0.1g, the initial toluene concentration was 100ppm, and 500W/cm was irradiated with a xenon lamp 2 After 3 hours of reaction, the conversion rate of toluene reaches 31% (see FIG. 7), and the final reaction environment temperature is 153 ℃, which shows that the ZnMn2O4 catalyst with the {1-1-1} crystal face exposed prepared by the method has general photo-thermal catalytic activity.
The above embodiments can be seen from the following examples:
ZnMn with {010} crystal face exposed can be prepared by adding N-N dimethylformamide and oxalic acid in ethanol solvent, and calcining at 170 ℃ and 600 ℃ solvothermal 2 O 4 A catalyst; znMn with exposed {11-1} crystal face can be prepared by adding oxalic acid to a mixed solution of ethanol and water, and calcining at 170 ℃ and 600 ℃ solvothermal 2 O 4 A catalyst; znMn with exposed {1-1-1} crystal face can be prepared by adding sodium bicarbonate solution to a mixed solution of n-hexane and n-pentanol, and calcining at 600 deg.C 2 O 4 A catalyst.
Above mentionedIn each example, znMn is prepared 2 O 4 The photocatalytic activity of the catalyst was evaluated by toluene gas conversion;
the test procedure was as follows: the catalytic activity of the catalyst was tested in a photo-thermal fluid bed reactor flowing continuously at atmospheric pressure. The reaction mixture gas is composed of toluene, air (O) 2 And N 2 ) Composition is prepared. Toluene gas was obtained from a compressed gas cylinder and had a concentration of 200ppm (N 2 As a dilution gas). The various gases were first mixed in a mixer, the toluene concentration was diluted to 100ppm with dry air, the flow rate of the mixed gas was controlled by a mass flow meter, the total flow rate was controlled at 50 mL/min, and the space velocity (GHSV) was maintained at 30,000 mL/(gh). Then, the mixed gas enters a double-layer quartz reaction tube, wherein a flat quartz tube is arranged in the double-layer quartz reaction tube, and the height of a middle gap is 20mm, the width is 15mm and the thickness is 10mm; the inner diameter is 4mm, the outer diameter is 8mm, and the total length is 40mm. A sample of 0.1g of the catalyst was weighed, then packed in the middle of the reaction tube and quartz wool was plugged into the bottom end of the center of the tube. The quartz reaction tube was placed in a reaction furnace having light source windows on both left and right sides, the middle part of the quartz reaction tube was irradiated with a xenon light source to perform a photo-thermal reaction, toluene and carbon dioxide in the outlet gas were detected by using gas chromatography (GC-9560, huaa i) equipped with a methane converter and a flame ionization detector, and in order to facilitate comparison of the catalytic activities of all samples, the photo-thermal catalytic activities of the samples were evaluated by using the relationship between toluene conversion and reaction time. ZnMn compared with the exposed {11-1} crystal face and the exposed {1-1-1} crystal face 2 O 4 The catalyst of the invention can be controllably synthesized into ZnMn with {010} crystal face exposed 2 O 4 The catalyst generates more active species in the catalytic oxidation of toluene, so that the reaction is easier to carry out, and the catalyst has excellent catalytic oxidation activity of toluene.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (5)

1. ZnMn with exposed crystal face 2 O 4 The application of the catalyst is characterized by comprising the following steps:
s100 is Mn (CH) 3 COO) 2 ·4H 2 O and Zn (CH) 3 COO) 2 ·2H 2 O is taken as a raw material, oxalic acid, ethanol and N-N dimethylformamide solution are added, and ZnMn is obtained through solvothermal reaction 2 O 4 A precursor;
s200, znMn 2 O 4 The precursor is subjected to the conditions of 600 ℃ and air to obtain ZnMn with exposed {010} crystal face 2 O 4 Catalyst, znMn with the exposed crystal face 2 O 4 And (3) carrying out photo-thermal catalytic oxidation on the toluene by using a catalyst.
2. ZnMn with exposed crystal face according to claim 1 2 O 4 The application of the catalyst is characterized in that the reaction temperature of the solvothermal reaction is 140-200 ℃ and the reaction time is 5-20h.
3. ZnMn with exposed crystal face according to claim 1 2 O 4 The application of the catalyst is characterized in that the volume ratio of the ethanol to the N-N dimethylformamide is 3:2, and the oxalic acid content is 1-2g.
4. ZnMn with exposed crystal face according to claim 1 2 O 4 The application of the catalyst is characterized in that the S200 specifically comprises the following steps:
ZnMn is added into 2 O 4 The precursor is placed in a muffle furnace, heated for a certain time, cooled to room temperature after finishing, and ZnMn with {010} crystal face exposed is obtained 2 O 4 A catalyst.
5. ZnMn with exposed crystal face according to claim 4 2 O 4 The application of the catalyst is characterized in that the heating is kept for a certain time, specifically, the heating rate is 2 ℃/min, the temperature is raised to 600 ℃, and the constant temperature of 600 ℃ is keptCalcining for 2-10h.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107792887A (en) * 2017-11-23 2018-03-13 江苏理工学院 A kind of high-specific surface area ZnMn2O4Preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107792887A (en) * 2017-11-23 2018-03-13 江苏理工学院 A kind of high-specific surface area ZnMn2O4Preparation method

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* Cited by examiner, † Cited by third party
Title
Huili Cao et al.，.Morphology engineering of self-assembled porous zinc manganate hexagons for lithium ion storage.《Electrochimica Acta》.2019,第330卷全文. *

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