CN113634271A - Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof - Google Patents
Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113634271A CN113634271A CN202110809281.5A CN202110809281A CN113634271A CN 113634271 A CN113634271 A CN 113634271A CN 202110809281 A CN202110809281 A CN 202110809281A CN 113634271 A CN113634271 A CN 113634271A
- Authority
- CN
- China
- Prior art keywords
- photo
- solution
- thermal
- mof
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012921 cobalt-based metal-organic framework Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000746 purification Methods 0.000 title claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 229910002451 CoOx Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 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 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 17
- 238000001228 spectrum Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and a preparation method and application thereof. The method comprises the following steps: (1) preparing Co-MOFs by taking pyridine-3, 5-dicarboxylic acid, cobalt nitrate and sodium hydroxide as raw materials through a room-temperature stirring method; (2) setting the Co-MOFs at N2Pyrolyzing under inert atmosphere to obtain Co/CoOxa/NC photo-thermal catalyst. The photo-thermal catalyst prepared by the invention can simultaneously absorb full spectrum and convert the full spectrum into heat energy, thereby inducing the reaction of photo-thermal catalytic purification of VOCs. Due to plasma metal Co, CoOxAnd the photo-thermal effect is enhanced by coupling of porous carbon, and the photo-thermal catalyst shows high-efficiency VOCs oxidation performance under the irradiation of sunlight and has good stability. The invention has simple and feasible process, high catalytic efficiency and low energy consumption in the catalytic processThe solar energy is directly used as a light and heat source, and the solar energy heat source has wide application prospect in the field of environmental energy.
Description
Technical Field
The invention belongs to the technical field of environment function materials, and particularly relates to a Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) are important precursors causing air pollution, can participate in atmospheric photochemical reactions, cause formation of ozone, photochemical smog and secondary aerosol in atmospheric environment, seriously harm human health and sustainable development of society, and therefore are receiving wide attention. At present, the traditional thermal catalysis has high efficiency in removing VOCs, but mainly relies on electric energy to provide working temperature, and has huge energy consumption. The photocatalysis technology is a technology for degrading pollutants by utilizing clean solar drive, but the light energy utilization rate is low, and the oxidation is not thorough, so that the wide practical application of the photocatalysis technology is greatly limited. Therefore, it is urgently needed to develop a green technology which perfectly combines the high degradation efficiency of thermal catalysis and the low energy consumption of photocatalysis to realize the green and low-energy-consumption treatment of the VOCs.
In recent years, the emerging photo-thermal catalytic oxidation is a technology for efficiently purifying VOCs by utilizing solar energy to store, convert and drive catalytic reaction. The method is not limited by the spectrum range any more, can effectively utilize full spectrum energy, particularly infrared light, and can obtain high-efficiency durable catalytic performance equivalent to that of thermal catalysis without secondary energy input. However, most of the current photo-thermal catalysts have narrow solar absorption spectrum and low photo-thermal conversion efficiency, and the catalytic efficiency is still not ideal compared with the traditional thermal catalysis and photo-catalysis technologies. Therefore, it becomes a challenge to develop a photo-thermal catalyst with high activity and high full-spectrum light absorption capability, improve the photo-thermal conversion efficiency, and realize the efficient degradation of VOCs. In addition, due to the high cost of noble metal-based catalysts, there is increasing interest in transition metal catalysts that are cost-effective. The transition metal has strong Localized Surface Plasmon Resonance (LSPR) effect and can drive redox reaction under the irradiation of sunlight. While the carbon-based MOFs (metal organic frameworks) derivative porous material obtained by taking MOFs as a precursor has high gas adsorption capacity, full spectrum light absorption capacity and enhanced chemical stability, and is concerned.
In view of the above, the invention firstly prepares Co-MOFs by taking pyridine-3, 5-dicarboxylic acid, cobalt nitrate and sodium hydroxide as raw materials through a room-temperature stirring self-assembly method; then, the Co-MOFs is added into N2Pyrolyzing the mixture in inert atmosphere to obtain Co and CoOxN-doped C-composition composite material (named Co/CoO)x/NC). Such Co/CoOxthe/NC material has a unique mixed interface structure, so that the plasma metal Co and CoOxThe N-doped C has strong interaction with N atoms, so that the light absorption range of the N-doped C can be expanded to an infrared region, and the key problems of narrow sunlight absorption spectrum, low photothermal conversion efficiency and the like of the conventional photothermal catalyst for photothermal catalysis can be effectively solved. Meanwhile, the highly dispersed Co-N-C sites of the material are easy to adsorb and enrich VOCs molecules to active sites of the material, and efficient adsorption-catalysis integration is realized. The invention provides a new idea for the fields of preparation of high-efficiency solar-driven environmental purification catalysts, atmospheric pollution control and the like.
Disclosure of Invention
The invention aims to overcome the problems of narrow sunlight absorption spectrum, low photothermal conversion efficiency and the like of a photothermal catalyst, and provides Co/CoO with light absorption capacity, high activity and controllable structurexPreparation method and application of/NC photo-thermal catalyst. Compared with the original Co-MOFs, the prepared photo-thermal catalyst has obviously improved performances such as sunlight absorption capacity, photo-thermal conversion efficiency, catalytic activity, catalytic stability and the like.
The purpose of the invention is realized by the following technical scheme:
is used forA preparation method of a Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs is characterized in that pyridine-3, 5-dicarboxylic acid, cobalt nitrate and sodium hydroxide are placed in an organic solvent, and the Co/CoO is prepared by stirring at room temperature, centrifugal washing, vacuum drying and calcining in a tubular furnacex(ii) a/NC photothermal catalyst; the photo-thermal catalyst has a unique mixed interface structure, and under the irradiation of sunlight, plasma metal Co and CoOxThe N-doped C has strong interaction with N atoms, and can efficiently absorb full-spectrum energy and convert the full-spectrum energy into heat energy, so that the reaction of purifying VOCs by photo-thermal catalysis is induced, and the reaction rate and the catalytic performance are improved.
The preparation method comprises the following steps:
(1) preparation of Co-MOF:
mixing 45-55 mL of water with 45-55 mL of organic solution to obtain a solution A, stirring at room temperature for 5-10 min, adding 6.5-7.5 g of cobalt nitrate to the solution A, and mixing and stirring until the cobalt nitrate is dissolved to obtain a solution B; then, mixing 145-155 mL of water with 145-155 mL of organic solution to obtain a solution C, stirring at room temperature for 5-10 min, adding 0.7-1.7 g of sodium hydroxide to the solution C, mixing and stirring until the sodium hydroxide is dissolved to obtain a solution D, adding 1.9-2.9 g of pyridine-3, 5-dicarboxylic acid to the solution D, and then performing ultrasonic mixing uniformly to obtain a solution E; transferring the solution B into the solution E, stirring at room temperature for 10-14h to obtain a solution F, filtering to obtain pink precipitates, centrifugally washing the precipitates with deionized water and ethanol, and drying to obtain Co-MOF;
(2)Co/CoOxpreparation of/NC:
drying the Co-MOF prepared in the step (1) in an oven, then placing the Co-MOF in a tube furnace, calcining for 3-6 h at a constant heating rate of 400-600 ℃ in an inert atmosphere, and naturally cooling to room temperature to obtain Co/CoOxNC photo-thermal catalytic material.
Further, in the step (1), the organic solvent is acetonitrile;
further, in the step (1), the stirring temperature at room temperature is 25-35 ℃; the stirring speed is 50-100 r/min; the ultrasonic time is 0.5-1 h, and the ultrasonic temperature is 25-35 ℃; the ultrasonic frequency is 35-40 KHz, and the ultrasonic power is 520-560W; the centrifugal rate of the product is 3500-4500 rpm; the drying temperature is 60-80 ℃, and the drying time is 4-6 h;
further, in the step (2), the inert atmosphere is nitrogen, the heating rate is 0.5-1.5 ℃/min, and the cooling rate is 1-10 ℃/min.
A Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs is applied to the field of degradation of volatile organic compounds. Co/CoOxthe/NC photo-thermal catalyst can stably degrade volatile organic compounds under full spectrum without consuming secondary energy such as electric energy for heat supply.
The material prepared by the invention is essentially different from the existing material, and the Co-MOFs is prepared by a room temperature stirring method and then calcined in a tubular furnace under the inert atmosphere to obtain Co/CoO with high sunlight absorption capacityxa/NC photo-thermal catalyst. The photo-thermal catalyst has a unique mixed interface structure, and under the irradiation of sunlight, plasma metal Co and CoOxThe catalyst has strong interaction with C doped with N atoms, can widen the light absorption range of the material and improve the photo-thermal conversion efficiency, and simultaneously, Co-N-C is used as a target active site of the photo-thermal catalytic oxidation reaction of VOCs to realize the catalytic performance with high efficiency and high stability.
Therefore, compared with the prior art, the invention has the advantages that:
Co/CoO of the inventionxThe preparation method of the/NC has the advantages of simple and convenient operation, simple process, good repeatability and the like. In addition, the prepared material has high-dispersion Co-N-C sites, VOCs molecules are easy to adsorb and enrich to active sites of the material, and simultaneously, plasma metal Co and CoO are adoptedxThe mixed interface of the N-doped C increases the absorption of sunlight and improves the photo-thermal conversion efficiency, so that Co/CoOxthe/NC hybrid material realizes high-efficiency and long-time stable catalytic performance in the reaction of degrading VOCs by photo-thermal catalysis completely depending on solar energy.
Drawings
FIG. 1 is a graph showing UV-VIS-IR absorption spectra of photothermal catalysts prepared in examples 1, 2 and 3 of the present invention;
FIG. 2 shows the photo-thermal catalyst prepared by the method 1, 2, 3 at 300mW/cm2A material thermal effect diagram under the irradiation of a full-spectrum xenon lamp light source;
FIG. 3 shows the photo-thermal catalyst prepared in examples 1, 2 and 3 of the present invention at 300mW/cm2And (3) an activity comparison graph of the catalyst on the photo-thermal catalytic oxidation of the methanol under the irradiation of a full-spectrum xenon lamp light source.
FIG. 4 shows the photo-thermal catalyst prepared in example 2 of the present invention at 300mW/cm2And (3) a stability graph of the catalyst on the photo-thermal catalytic oxidation of the methanol under the condition of irradiating for 50 hours by a full-spectrum xenon lamp light source.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
The preparation method comprises the following steps:
(1) preparation of Co-MOF:
mixing 45-55 mL of water with 45-55 mL of organic solution to obtain a solution A, stirring at room temperature for 5-10 min, adding 6.5-7.5 g of cobalt nitrate to the solution A, and mixing and stirring until the cobalt nitrate is dissolved to obtain a solution B; then, mixing 145-155 mL of water with 145-155 mL of organic solution to obtain a solution C, stirring at room temperature for 5-10 min, adding 0.7-1.7 g of sodium hydroxide to the solution C, mixing and stirring until the sodium hydroxide is dissolved to obtain a solution D, adding 1.9-2.9 g of pyridine-3, 5-dicarboxylic acid to the solution D, and then performing ultrasonic mixing uniformly to obtain a solution E; transferring the solution B into the solution E, stirring at room temperature for 10-14h to obtain a solution F, filtering to obtain pink precipitates, centrifugally washing the precipitates with deionized water and ethanol, and drying to obtain Co-MOF;
(2)Co/CoOxpreparation of/NC:
drying the Co-MOF prepared in the step (1) in an oven, then placing the Co-MOF in a tube furnace, calcining for 3-6 h at a constant heating rate of 400-600 ℃ in an inert atmosphere, and naturally cooling to room temperature to obtain Co/CoOxNC photo-thermal catalytic material.
In the step (1), the organic solvent is acetonitrile.
In the step (1), the stirring temperature at room temperature is 25-35 ℃; the stirring speed is 50-100 r/min; the ultrasonic time is 0.5-1 h, and the ultrasonic temperature is 25-35 ℃; the ultrasonic frequency is 35-40 KHz, and the ultrasonic power is 520-560W; the centrifugal rate of the product is 3500-4500 rpm; the drying temperature is 60-80 ℃, and the drying time is 4-6 h.
Further, in the step (2), the inert atmosphere is nitrogen, the heating rate is 0.5-1.5 ℃/min, and the cooling rate is 1-10 ℃/min.
Example 1
Preparation of Co-MOF: mixing 50mL of water and 50mL of acetonitrile to obtain a solution A, stirring at room temperature for 5-10 min, adding 7g of cobalt nitrate into the solution A, and mixing and stirring until the cobalt nitrate is dissolved to obtain a solution B; then, mixing 150mL of water with 150mL of acetonitrile to obtain a solution C, stirring for 5min at room temperature, adding 1.2g of sodium hydroxide into the solution C, mixing and stirring until the sodium hydroxide is dissolved to obtain a solution D, adding 2.4g of pyridine-3, 5-dicarboxylic acid into the solution D, and then performing ultrasonic mixing uniformly to obtain a solution E; and transferring the solution B into the solution E, stirring at room temperature for 12h to obtain a solution F, filtering to obtain pink precipitate, centrifugally washing the precipitate with deionized water and ethanol, and drying to obtain Co-MOF.
Co/CoOxPreparation of/NC-400: the prepared Co-MOF was dried in an oven, and then 1.2g of Co-MOF was placed in a tube furnace under N2Calcining at the temperature rising rate of 1 ℃/min to 400 ℃ for 4h in the atmosphere, and naturally cooling to room temperature to obtain Co/CoOxNC-400 photo-thermal catalytic material.
Example 2
Preparation of Co-MOF: mixing 50mL of water and 50mL of acetonitrile to obtain a solution A, stirring at room temperature for 5-10 min, adding 7g of cobalt nitrate into the solution A, and mixing and stirring until the cobalt nitrate is dissolved to obtain a solution B; then, mixing 150mL of water with 150mL of acetonitrile to obtain a solution C, stirring for 5min at room temperature, adding 1.2g of sodium hydroxide into the solution C, mixing and stirring until the sodium hydroxide is dissolved to obtain a solution D, adding 2.4g of pyridine-3, 5-dicarboxylic acid into the solution D, and then performing ultrasonic mixing uniformly to obtain a solution E; and transferring the solution B into the solution E, stirring at room temperature for 12h to obtain a solution F, filtering to obtain pink precipitate, centrifugally washing the precipitate with deionized water and ethanol, and drying to obtain Co-MOF.
Co/CoOxPreparation of/NC-500: the prepared Co-MOF was dried in an oven, and then 1.2g of Co-MOF was placed in a tube furnace under N2Calcining at 1 deg.C/min to 500 deg.C for 4h, and naturally cooling to room temperature to obtain Co/CoOxNC-500 photo-thermal catalytic material.
Example 3
Preparation of Co-MOF: mixing 50mL of water and 50mL of acetonitrile to obtain a solution A, stirring at room temperature for 5-10 min, adding 7g of cobalt nitrate into the solution A, and mixing and stirring until the cobalt nitrate is dissolved to obtain a solution B; then, mixing 150mL of water with 150mL of acetonitrile to obtain a solution C, stirring for 5min at room temperature, adding 1.2g of sodium hydroxide into the solution C, mixing and stirring until the sodium hydroxide is dissolved to obtain a solution D, adding 2.4g of pyridine-3, 5-dicarboxylic acid into the solution D, and then performing ultrasonic mixing uniformly to obtain a solution E; and transferring the solution B into the solution E, stirring at room temperature for 12h to obtain a solution F, filtering to obtain pink precipitate, centrifugally washing the precipitate with deionized water and ethanol, and drying to obtain Co-MOF.
Co/CoOxPreparation of/NC-600: the prepared Co-MOF was dried in an oven, and then 1.2g of Co-MOF was placed in a tube furnace under N2Calcining at a heating rate of 1 ℃/min to 600 ℃ for 4h in the atmosphere, and naturally cooling to room temperature to obtain Co/CoOxthe/NC-600 photo-thermal catalytic material.
Example 4
And (3) material characterization and analysis: from FIG. 1, it can be observed that the Co-MOF derived Co/CoO of the present inventionx/NC-400，Co/CoOxNC-500 and Co/CoOxthe/NC-600 has strong absorption to ultraviolet light, visible light and infrared radiation, and the Co/CoOxThe absorption of/NC is significantly greater than that of Co-MOF. Co/CoO with increasing calcination temperaturexThe sunlight absorbing ability of/NC gradually increases. Indicating the Co/CoO of the inventionxthe/NC has high full-spectrum light absorption capability.
Evaluation of photothermal catalytic oxidation activity: methanol is used as a probe molecule to explore the photo-thermal catalytic activity of the catalyst. The photothermal catalytic oxidation methanol degradation reaction is carried out on a self-made fixed bed reactor, the light source used in the reaction is PLS-SXE300 full spectrum xenon lamp light source of Beijing Pofely science and technology Limited company, and the reaction light rate density is 300mW/m2The methanol concentration is 200ppm, the catalyst dosage is 100mg, the reaction gas flow rate is 100mL/min, the space velocity is 60000 mL/g.h, and N is2Is a balance gas; concentration change of methanol during the reaction and final product CO2The concentration value of (b) is detected on-line by gas chromatography with FID detector. The experimental results according to FIG. 2 show that under simulated solar irradiation, the material reaches high temperature in a short time, Co/CoOx/NC-400， Co/CoOxNC-500 and Co/CoOxThe temperatures of the/NC-600 platforms are 132 ℃, 171 ℃ and 170 ℃ respectively, which shows that the prepared photo-thermal catalyst has higher solar photo-thermal conversion efficiency. From the results of the activity test in FIG. 3, it can be seen that Co/CoO was contained in all the catalysts preparedxthe/NC-500 shows the best catalytic activity, the conversion rate of the methanol can reach 97 percent, and the high activity is kept in the irradiation process; the activity of Co-MOF is the worst, and the conversion rate of methanol is only about 21%. The long term stability test results according to FIG. 4 show that Co/CoOxThe performance of the/NC-500 continuous irradiation for 50 hours is almost unchanged, the average conversion rate of the methanol is 97 percent, and the CO content is reduced2The yield is 95%, which shows that the product has excellent photo-thermal catalytic oxidation stability.
The above examples 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. Preparation of Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCsThe preparation method is characterized in that pyridine-3, 5-dicarboxylic acid, cobalt nitrate and sodium hydroxide are placed in an organic solvent, and the Co/CoO is prepared by stirring at room temperature, centrifugally washing, vacuum drying and calcining in a tube furnacex(ii) a/NC photothermal catalyst; the photo-thermal catalyst can absorb full spectrum and convert the full spectrum into heat energy, so that the reaction of photo-thermal catalytic purification of VOCs is induced.
2. The method of claim 1, wherein the method comprises the steps of:
(1) preparation of Co-MOF:
mixing water and an organic solvent to obtain a solution A, stirring at room temperature, adding cobalt nitrate into the solution A, and mixing and stirring until the cobalt nitrate is dissolved to obtain a solution B; then, mixing water and an organic solvent to obtain a solution C, stirring at room temperature, adding sodium hydroxide into the solution C, mixing and stirring until the sodium hydroxide is dissolved to obtain a solution D, adding pyridine-3, 5-dicarboxylic acid into the solution D, and then uniformly mixing by ultrasound to obtain a solution E; transferring the solution B into the solution E, stirring at room temperature to obtain a solution F, filtering to obtain pink precipitates, centrifugally washing the precipitates with deionized water and ethanol, and drying to obtain Co-MOF;
(2)Co/CoOxpreparation of/NC:
drying the Co-MOF prepared in the step (1) in an oven, then placing the Co-MOF in a tube furnace, calcining for 3-6 h at a constant heating rate of 400-600 ℃ in an inert atmosphere, and naturally cooling to room temperature to obtain Co/CoOxNC photo-thermal catalytic material.
3. The method for preparing a Co-MOF derivative photothermal catalyst for photothermal catalytic purification of VOCs according to claim 2, wherein in step (1), the organic solvent is acetonitrile.
4. The method for preparing a Co-MOF derivative photothermal catalyst for photothermal catalytic purification of VOCs according to claim 2, wherein in the step (1), the addition amount of water and the organic solvent in the solution A satisfies the following conditions: the addition amount of water is: 45-55 mL of water; the addition amount of the organic solvent is as follows: 45-55 mL; in the solution B, the addition amount of cobalt nitrate is as follows: 6.5-7.5 g.
5. The method for preparing a Co-MOF derivative photothermal catalyst for photothermal catalytic purification of VOCs according to claim 2, wherein in the step (1), the addition amount of water and the organic solvent in the solution C satisfies the following condition: the addition amount of water is: 145-155 mL of water; the addition amount of the organic solvent is as follows: 145-155 mL.
6. The preparation method of the Co-MOF derivative photothermal catalyst for photothermal catalytic purification of VOCs according to claim 2, wherein in the step (1), the addition amount of sodium hydroxide is 0.7-1.7 g; the amount of pyridine-3, 5-dicarboxylic acid added is 1.9 to 2.9 g.
7. The preparation method of the Co-MOF derivative photothermal catalyst for photothermal catalytic purification of VOCs according to claim 2, wherein in the step (1), the temperature of stirring at room temperature is 25-35 ℃; the stirring speed is 50-100 r/min; when the solution B and the solution D are prepared, the stirring time is 5-10 min; when the solution F is prepared, the stirring time is 10-14 h;
the ultrasonic time is 0.5-1 h, and the ultrasonic temperature is 25-35 ℃; the ultrasonic frequency is 35-40 KHz, and the ultrasonic power is 520-560W; the centrifugal rate of the product is 3500-4500 rpm; the drying temperature is 60-80 ℃, and the drying time is 4-6 h.
8. The preparation method of the Co-MOF derivative photothermal catalyst for photothermal catalytic purification of VOCs according to claim 2, wherein in the step (2), the inert atmosphere is nitrogen, the temperature rise rate is 0.5-1.5 ℃/min, and the temperature drop rate is 1-10 ℃/min.
9. A Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs is prepared by the preparation method of any one of claims 1-8.
10. The application of Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs in the field of degradation of volatile organic compounds as claimed in claim 5, wherein Co/CoOxthe/NC photo-thermal catalyst can stably degrade volatile organic compounds under full spectrum without consuming secondary energy such as electric energy for heat supply.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110809281.5A CN113634271B (en) | 2021-07-16 | 2021-07-16 | Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110809281.5A CN113634271B (en) | 2021-07-16 | 2021-07-16 | Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113634271A true CN113634271A (en) | 2021-11-12 |
| CN113634271B CN113634271B (en) | 2022-06-10 |
Family
ID=78417746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110809281.5A Active CN113634271B (en) | 2021-07-16 | 2021-07-16 | Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113634271B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150291870A1 (en) * | 2012-08-15 | 2015-10-15 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| CN106064087A (en) * | 2016-06-08 | 2016-11-02 | 南京工业大学 | A kind of method preparing VOCs catalyst for catalytic combustion |
| CN106582850A (en) * | 2017-01-05 | 2017-04-26 | 福州大学化肥催化剂国家工程研究中心 | Novel preparation method for Co-MOF catalyst and application of catalyst |
| CN106944092A (en) * | 2017-04-22 | 2017-07-14 | 武汉理工大学 | A kind of Fe MnO with efficient photo-thermal concerted catalysis purifying VOCs2The preparation method of catalyst |
| CN107739442A (en) * | 2017-09-25 | 2018-02-27 | 桂林理工大学 | The synthesis and application for the metal organic framework compound constructed based on the dicarboxylic acids of pyridine 2,5 and 4,4 ' bipyridyls |
| JPWO2016185679A1 (en) * | 2015-05-15 | 2018-03-01 | パナソニック株式会社 | Chemical sensor |
| CN107824210A (en) * | 2017-09-15 | 2018-03-23 | 广东工业大学 | A kind of titanium dioxide composite photocatalyst of N doping mesoporous carbon parcel and its preparation method and application |
| CN107983329A (en) * | 2017-11-22 | 2018-05-04 | 华南理工大学 | It is a kind of using metal organic framework as cerium-based composite oxides VOCs combustion catalysts of template and preparation method thereof |
| CN108525675A (en) * | 2018-04-08 | 2018-09-14 | 上海应用技术大学 | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination |
| BR112018074691A2 (en) * | 2016-06-13 | 2019-03-12 | Basf Corp | processes for the preparation of a catalyst, catalyst, method for selective catalytic reduction of nox and use of catalyst |
| CN109647477A (en) * | 2018-11-26 | 2019-04-19 | 大连理工大学 | A kind of fast preparation method and application of the derivative catalyst of high yield MOF |
| CN109647407A (en) * | 2019-02-12 | 2019-04-19 | 济南大学 | A kind of preparation method and application based on bimetallic MOF nanocrystalline composite material |
| CN109759110A (en) * | 2019-01-03 | 2019-05-17 | 华南理工大学 | A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof |
| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
| CN111569929A (en) * | 2020-05-18 | 2020-08-25 | 石河子大学 | Co-MOF derived cobalt/nitrogen/carbon composite material and preparation method thereof |
| CN111883785A (en) * | 2020-08-12 | 2020-11-03 | 广西师范大学 | Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof |
-
2021
- 2021-07-16 CN CN202110809281.5A patent/CN113634271B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150291870A1 (en) * | 2012-08-15 | 2015-10-15 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| JPWO2016185679A1 (en) * | 2015-05-15 | 2018-03-01 | パナソニック株式会社 | Chemical sensor |
| CN106064087A (en) * | 2016-06-08 | 2016-11-02 | 南京工业大学 | A kind of method preparing VOCs catalyst for catalytic combustion |
| BR112018074691A2 (en) * | 2016-06-13 | 2019-03-12 | Basf Corp | processes for the preparation of a catalyst, catalyst, method for selective catalytic reduction of nox and use of catalyst |
| CN106582850A (en) * | 2017-01-05 | 2017-04-26 | 福州大学化肥催化剂国家工程研究中心 | Novel preparation method for Co-MOF catalyst and application of catalyst |
| CN106944092A (en) * | 2017-04-22 | 2017-07-14 | 武汉理工大学 | A kind of Fe MnO with efficient photo-thermal concerted catalysis purifying VOCs2The preparation method of catalyst |
| CN107824210A (en) * | 2017-09-15 | 2018-03-23 | 广东工业大学 | A kind of titanium dioxide composite photocatalyst of N doping mesoporous carbon parcel and its preparation method and application |
| CN107739442A (en) * | 2017-09-25 | 2018-02-27 | 桂林理工大学 | The synthesis and application for the metal organic framework compound constructed based on the dicarboxylic acids of pyridine 2,5 and 4,4 ' bipyridyls |
| CN107983329A (en) * | 2017-11-22 | 2018-05-04 | 华南理工大学 | It is a kind of using metal organic framework as cerium-based composite oxides VOCs combustion catalysts of template and preparation method thereof |
| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
| CN108525675A (en) * | 2018-04-08 | 2018-09-14 | 上海应用技术大学 | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination |
| CN109647477A (en) * | 2018-11-26 | 2019-04-19 | 大连理工大学 | A kind of fast preparation method and application of the derivative catalyst of high yield MOF |
| CN109759110A (en) * | 2019-01-03 | 2019-05-17 | 华南理工大学 | A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof |
| CN109647407A (en) * | 2019-02-12 | 2019-04-19 | 济南大学 | A kind of preparation method and application based on bimetallic MOF nanocrystalline composite material |
| CN111569929A (en) * | 2020-05-18 | 2020-08-25 | 石河子大学 | Co-MOF derived cobalt/nitrogen/carbon composite material and preparation method thereof |
| CN111883785A (en) * | 2020-08-12 | 2020-11-03 | 广西师范大学 | Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YOUPENG LI ET AL.: ""High pyridine N-doped porous carbon derived from metal–organic frameworks for boosting potassium-ion storage"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 袁会芳 等: ""Co-MOF衍生Co-N-C催化剂的制备及其氧还原性能研究"", 《功能材料》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113634271B (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zeng et al. | Investigation of promotion effect of Cu doped MnO2 catalysts on ketone-type VOCs degradation in a one-stage plasma-catalysis system | |
| CN110975857B (en) | Three-dimensional ordered macroporous oxygen-deficient cerium dioxide catalyst and preparation method and application thereof | |
| CN113000046A (en) | Modified manganese-based mullite catalyst for synergistic purification of nitrogen oxides and volatile organic compounds, and preparation method and application thereof | |
| CN111215067B (en) | Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst | |
| CN106179393B (en) | A kind of preparation method of manganese copper-based catalysts for the VOCs that degrades | |
| CN111151285A (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| Liao et al. | Constructing MOFs-derived Co3O4 microsphere with atomic pn homojunction as an efficient photothermal catalyst for boosting ethyl acetate oxidation under light irradiation | |
| CN111957333A (en) | Yb (Yb)2O3/g-C3N4Preparation method and application of bifunctional catalyst | |
| CN109745982A (en) | The preparation method and application of CeO 2 supporting copper oxide nano material | |
| Mo et al. | Uncovering the role of unsaturated coordination defects in manganese oxides for concentrated solar-heating photothermal OVOCs oxidation: Experimental and DFT explorations | |
| CN111359644B (en) | Non-noble metal-based molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production and preparation method and application thereof | |
| CN113634271B (en) | Co-MOF derivative photo-thermal catalyst for photo-thermal catalytic purification of VOCs, and preparation method and application thereof | |
| XUE et al. | Two-dimensional gC 3N4 compositing with Ag-TiO2 as deactivation resistant photocatalyst for degradation of gaseous acetaldehyde | |
| CN113769757B (en) | In-situ photothermal preparation of spinel structure Cu 1.5 Mn 1.5 O 4 Method for preparing catalyst and application thereof | |
| Zeng et al. | Synergistic photothermal catalytic oxidation of methanol and toluene mixture over Co-MOFs-derived catalyst: Interfacial and promotion effects | |
| CN116903021A (en) | Porous cerium oxide nano-sheet catalyst, preparation thereof and application thereof in photo-thermal synergistic carbon dioxide decomposition reaction | |
| CN109772423B (en) | Phosphorus and bismuth co-doped porous graphite phase carbon nitride photocatalyst and application thereof | |
| CN114452998B (en) | Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material | |
| CN110756189B (en) | Co with full solar spectrum response3O4/rGO composite catalyst, preparation method and photo-thermal catalysis application thereof | |
| CN116120505A (en) | Halogen-containing pyrenyl covalent organic framework polymer photocatalyst, and preparation method and application thereof | |
| CN115155624A (en) | Heterojunction composite material for visible light catalysis aldehyde removal, preparation method thereof and method for visible light catalysis degradation of VOCs | |
| Zhang et al. | Effect of calcination temperature on catalytic activity and textual property of Cu/HMOR catalysts in dimethyl ether carbonylation reaction | |
| CN112473681A (en) | Synthesis of copper bismuthate/cerium oxide photocatalyst and purification of p-toluene and formaldehyde thereof | |
| Liu et al. | Investigation on removal of multi-component volatile organic compounds in a two-stage plasma catalytic oxidation system-Comparison of X (X= Cu, Fe, Ce and La) doped Mn2O3 catalysts | |
| Bi et al. | Light-induced phase transformation to two-dimensional amorphous spinel CoAlOx nanosheets as a tandem photothermal catalyst for efficient and durable toluene oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |