CN114570340A - Application of graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds - Google Patents
Application of graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds Download PDFInfo
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the field of VOCs adsorption and recovery, and discloses application of a graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds. The composite material is GO/MIL-101, and graphene oxide is ultrasonically dispersed in water to form GO suspension; adding the GO suspension and the Cr salt into a reaction kettle with polytetrafluoroethylene, uniformly stirring, and adding a terephthalic acid organic ligand and water; carrying out hydrothermal reaction for 6-16 h at 160-220 ℃, washing and drying to obtain the catalyst. The composite material can widen and enhance the light absorption range and intensity of the MOF, can absorb a large amount of light energy and convert the light energy into heat energy under the irradiation of light with the wavelength of 200-1200nm, excites the rapid desorption of the VOCs, and realizes the regeneration of the adsorbent. The method has the advantages of simple process, high desorption speed, low energy consumption and the like, is suitable for industrial production, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of atmospheric photocatalytic materials, and particularly relates to an application of a graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds.
Background
In recent years, as the quality of the atmospheric environment becomes worse and various environmental pollution events appear frequently, people pay more attention to the atmospheric pollution, and Volatile Organic Compounds (VOCs) which are an important atmospheric pollution source are also gradually hot spots for environmental research. VOCs are important preconditions causing urban dust haze and photochemical smog and mainly come from processes of coal, petrochemical industry, fuel combustion and the like, and most VOCs have toxicity, irritation, teratogenicity and carcinogenicity. Therefore, how to efficiently process the VOCs and improve the environmental quality becomes a research focus of researchers. Common treatment methods for VOCs include adsorption, absorption, catalytic oxidation and biological methods, wherein the adsorption method has the characteristics of simple operation, high efficiency and environmental protection, and can be applied to the treatment of high-concentration and low-concentration VOCs. However, the adsorbents (activated carbon, silica gel, molecular sieve, etc.) commonly used in industry have problems of small adsorption amount, difficult desorption, and difficult recycling of the adsorbents.
The metal organic framework Material (MOFs) is an organic-inorganic porous material consisting of inorganic secondary building units (metal oxide clusters or metal ions) and organic unit distribution sites, the coordination polymer provides remarkable chemical and structural diversity, and due to the characteristics of adjustable pore diameter, surface modification and the like, the metal organic framework material is superior to the traditional porous material in the aspect of adsorbing harmful gas/steam on the molecular level, and has many application cases in adsorbing and removing VOCs. However, due to the poor thermal conductivity of MOF itself, the most common thermal desorption technique has a low exposure rate and high energy consumption for desorbing VOCs. Graphene Oxide (GO) shows wide optical absorption and excellent photothermal conversion performance in visible light and Near Infrared (NIR) electromagnetic spectrum, and is widely applied to aspects of cancer treatment, seawater purification and the like, but graphene oxide is of a single-layer net structure, is low in specific surface area and porosity, and is limited in application in the aspect of adsorbing high-concentration VOCs. At present, the research on the application of photo-thermal conversion to adsorption and desorption of VOCs is still few.
Disclosure of Invention
In order to overcome the defects of small adsorption capacity, low solar energy utilization rate, low desorption efficiency, high desorption energy consumption and the like of the conventional common VOCs adsorbent, the invention mainly aims to provide the application of the graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds. The material has high photo-thermal conversion performance, can combine the photo-thermal conversion performance of graphene oxide and the porous adsorption characteristics of the MOF, can improve the regeneration performance of the material under the drive of sunlight, overcomes the defects of low solar energy utilization rate and low MOF desorption efficiency, and expands the application prospect of the MOF in the aspect of VOCs treatment.
The purpose of the invention is realized by the following technical scheme:
an application of a graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds is disclosed, wherein the composite material graphene oxide/metal organic framework composite material, which is abbreviated as GO/MIL-101, is formed by ultrasonically dispersing graphene oxide in water; and adding the GO suspension and the Cr salt into a reaction kettle with polytetrafluoroethylene, uniformly stirring, adding organic ligand terephthalic acid and water, heating to 160-220 ℃, carrying out hydrothermal reaction for 6-16 h, washing, and drying to obtain the graphene oxide.
Preferably, the graphene oxide is in a single-layer sheet shape, and the size of the graphene oxide is 500 nm-1 μm.
Preferably, the Cr salt is CrCl3·6H2O or Cr (NO)3)3·9H2O; the molar ratio of the Cr salt to the terephthalic acid to the water is 1: (1-2): (500-600); the mole ratio of graphene oxide to Cr salt in the GO suspension is (0.02-0.1): 1. the concentration of the GO suspension is 2-4 mg/mL.
Preferably, the rate of temperature rise is 0.1-1 ℃/min; the drying temperature is 80-120 ℃, and the drying time is 12-20 h.
Preferably, the light is in a region from ultraviolet to near infrared, and the wavelength of the light is 200-1200 nm.
Preferably, the volatile organic is ethyl acetate, toluene or styrene.
The mechanism that the graphene oxide/metal organic framework composite material can realize light-operated absorption and desorption of VOCs is as follows: the graphene oxide has adjustable physical properties and high environmental compatibility, can absorb spectra in visible light and near infrared regions, has full-spectrum light absorption performance, has large specific surface area and pore volume, can be used for adsorbing and enriching VOCs, and generally has narrow light absorption range. The photothermal conversion performance is weak. Therefore, the graphene oxide is combined with the metal organic framework material, the graphene oxide is firstly coordinated with the metal source, the light energy utilization rate and the regeneration performance of the composite material are effectively improved, a large amount of VOCs can be adsorbed, the photo-thermal conversion performance can be improved, the VOCs are desorbed, and the efficient treatment of the VOCs is realized.
The graphene oxide/metal organic framework composite material is applied to adsorption and desorption treatment of VOCs, graphene oxide covers the surface of the MOF, and the influence of a reticular honeycomb structure of the graphene oxide on the specific surface area of the MOF is small, so that the influence on the adsorption process is small. GO has excellent light absorption performance and heat conduction performance, compound the back with the MOF, this combined material not only remains the big adsorption capacity of MOF, and can widen and strengthen MOF's light absorption scope and intensity, under the light irradiation of 200 ~ 1200nm wavelength, can absorb a large amount of light energy and change into heat energy, because MOF grows on the GO surface, cause a large amount of heat energy that GO produced to experience shorter distance transmission to the MOF surface, arouse the quick desorption of being adsorbed VOCs, realize the high efficiency of adsorbent, quick regeneration. The light-operated adsorption technology can avoid long-distance heat transmission of traditional external source heating, and effectively solves the problem of poor heat conductivity of the MOF.
Compared with the prior art, the invention has the following advantages:
1. the composite material provided by the invention not only retains the large adsorption capacity of the MOF, but also can widen and enhance the light absorption range and strength of the MOF. Therefore, under the irradiation of sunlight, a large amount of light energy can be absorbed and converted into heat energy, the rapid desorption of VOCs is excited, and the regeneration of the adsorbent is realized. The single-layer sheet graphene oxide has adjustable physical properties and high environmental compatibility, is not easy to aggregate and pile in aqueous solution, and is beneficial to uniform growth of MOF on the surface of the MOF; the absorption performance of the spectrum in visible light and near infrared regions is good, and the light energy can be effectively converted into heat energy and transferred to the MOF under the drive of sunlight, so that the solar energy is efficiently utilized.
2. According to the invention, the graphene oxide/metal organic framework composite material is synthesized by a hydrothermal method, the condition is mild, and the carboxyl functional group on the surface of the graphene oxide can be fully stirred with Cr salt3+Preferentially coordinating, and then adding an organic ligand, so that the MOF can be effectively attached to the surface of the graphene oxide, the light absorption range of the MOF is widened, sunlight is effectively converted into heat to be transferred to the MOF, and the regeneration of the material is realized.
3. The GO/MIL-101 disclosed by the invention has good adsorption and desorption performances on VOCs (such as ethyl acetate). For volatile organic compounds (such as ethyl acetate) with medium and high concentration (200-2000 ppm), the VOCs (such as ethyl acetate) desorbed by GO/MIL-101 in 30min is more than 90% under the drive of sunlight.
4. Compared with the traditional desorption technologies such as temperature rising desorption, depressurization desorption and purging desorption, the graphene oxide/metal organic framework composite material has the advantages of simple process, high desorption speed, low energy consumption and the like when being applied to light-operated desorption of volatile organic compounds, is suitable for industrial production and has wide application prospect.
Drawings
FIG. 1 shows the photothermal conversion performance of GO/MIL-101 obtained in example 1 under the illumination of 200-1200nm wavelength.
FIG. 2 is a graph of the adsorption and desorption of GO/MIL-101 from ethyl acetate gas obtained in example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Preparation of composite materials
(1) Weighing 30mg of GO, and dispersing in 10mL of water by ultrasonic treatment for 6h to form 3mg/mL GO suspension;
(2) 5mL of GO suspension and CrCl were taken3·6H2Adding O into the reaction kettle, stirring and mixing for 1h, and then according to CrCl3·6H2O：C8H6O4: molar ratio of water to 1:1:500 (i.e. 0.4622g of CrCl were weighed out)3·6H2O、0.2853g C8H6O4And 10mL of water) is added into a high-pressure reaction kettle, the temperature is increased to 190 ℃ at the speed of 1 ℃/min, the hydrothermal reaction is carried out for 16h, the mixture is naturally cooled to room temperature, the DMF and the water are respectively filtered and filtered for three times, and the mixture is dried in vacuum at 100 ℃ for 12h, so that the graphene oxide/metal organic framework composite material, which is abbreviated as GO/MIL-101, is obtained; wherein GO is 2mol percent of GO/MIL-101.
2. Performance testing
Coating the GO/MIL-101 composite material on the surface of a sample reactor, simulating solar illumination by using a xenon lamp, and respectively recording the surface temperature change of the material under the irradiation of ultraviolet-visible light and ultraviolet-near infrared spectral regions by using an infrared camera. FIG. 1 shows the light-heat conversion performance of GO/MIL-101 obtained in this example under the sun illumination (200-1200 nm). As can be seen from FIG. 1, the GO/MIL-101 of the present invention can be raised to temperatures above 120 ℃ within 120 s. The graphene oxide can assist the MOF to exert a better photo-thermal conduction effect. FIG. 2 is a graph showing the adsorption and desorption of GO/MIL-101 from ethyl acetate gas obtained in example 1. As can be seen from FIG. 2, GO/MIL-101 can desorb ethyl acetate by more than 90% within 30 min. The result shows that the GO/MIL-101 composite material can improve the photo-thermal conversion performance of high-purity MOF, and is beneficial to realizing the high-efficiency and rapid regeneration of MOF.
Example 2
1. Weighing 30mg of GO, and dispersing in 10mL of water by ultrasonic treatment for 6h to form 3mg/mL GO suspension;
2. taking 10mL of GO suspension and CrCl3·6H2Adding O into the reaction kettle, stirring and mixing for 1h, and mixingPhoto CrCl3·6H2O：C8H6O4: molar ratio of water to 1:1:500 (i.e. 0.3806g of CrCl were weighed out)3·6H2O、0.2649g C8H6O4And 10mL of water) is added into a high-pressure reaction kettle, the temperature is increased to 190 ℃ at the speed of 1 ℃/min, the hydrothermal reaction is carried out for 16h, the mixture is naturally cooled to the room temperature, the DMF and the water are respectively filtered and filtered for three times, and the vacuum drying is carried out for 12h at the temperature of 100 ℃, so as to obtain the graphene oxide/metal organic framework composite material, which is abbreviated as GO/MIL-101. Wherein GO is 5mol percent of GO/MIL-101.
Coating the GO/MIL-101 composite material on the surface of a sample reactor, simulating solar illumination by using a xenon lamp, and respectively recording the surface temperature change of the material under the irradiation of ultraviolet-visible light and ultraviolet-near infrared spectral regions by using an infrared camera. The composite was raised to 88 ℃ and 137 ℃ at surface temperatures of 150s and 120s, respectively. The graphene oxide can assist the MOF to exert a better photo-thermal conduction effect.
Example 3
1. Weighing 60mg of GO, and dispersing in 20mL of water by ultrasonic for 6h to form 3mg/mL GO suspension;
2. 15mL of GO (0.04g) suspension and CrCl were taken3·6H2Adding O into the reaction kettle, stirring and mixing for 1h, and then according to CrCl3·H2O：C8H6O4: molar ratio of water to 1:1:500 (i.e. 0.3263gCrCl was weighed out)3·6H2O、0.2014g C8H6O4And 10mL of water) is added into a high-pressure reaction kettle, the temperature is increased to 190 ℃ at the speed of 1 ℃/min, the hydrothermal reaction is carried out for 16h, the mixture is naturally cooled to the room temperature, the DMF and the water are respectively filtered and filtered for three times, and the vacuum drying is carried out for 12h at the temperature of 100 ℃, so as to obtain the graphene oxide/metal organic framework composite material, which is abbreviated as GO/MIL-101. Wherein GO is 10mol percent of the GO/MIL-101 composite material.
Coating the GO/MIL-101 composite material on the surface of a sample reactor, simulating solar illumination by using a xenon lamp, and respectively recording the surface temperature change of the material under the irradiation of ultraviolet-visible light and ultraviolet-near infrared spectral regions by using an infrared camera. The composite was raised to 73 ℃ and 136 ℃ at surface temperatures of 100s and 80s, respectively. The graphene oxide can assist the MOF to exert a better photo-thermal conduction effect.
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 (6)
1. The application of the graphene oxide/metal organic framework composite material in optically controlled desorption of volatile organic compounds is characterized in that the composite material is a graphene oxide/metal organic framework composite material, which is abbreviated as GO/MIL-101, and graphene oxide is ultrasonically dispersed in water to form GO suspension; and adding the GO suspension and the Cr salt into a reaction kettle with polytetrafluoroethylene, uniformly stirring, adding organic ligand terephthalic acid and water, heating to 160-220 ℃, carrying out hydrothermal reaction for 6-16 h, washing, and drying to obtain the catalyst.
2. The application of the graphene oxide/metal organic framework composite material in photo-controlled desorption of volatile organic compounds according to claim 1, wherein the graphene oxide is in a single-layer sheet shape, and the size of the graphene oxide is 500 nm-1 μm.
3. The application of the graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds according to claim 1, wherein the Cr salt is CrCl3·6H2O or Cr (NO)3)3·9H2O; the molar ratio of the Cr salt to the terephthalic acid to the water is 1: (1-2): (500-600); the mole ratio of graphene oxide to Cr salt in the GO suspension is (0.02-0.1): 1; the concentration of the GO suspension is 2-4 mg/mL.
4. The application of the graphene oxide/metal organic framework composite material in the light-operated desorption of volatile organic compounds according to claim 1, wherein the temperature rise rate is 0.1-1 ℃/min; the drying temperature is 80-120 ℃, and the drying time is 12-20 h.
5. The application of the graphene oxide/metal organic framework composite material in optically controlled desorption of volatile organic compounds according to claim 1, wherein the light is in a region from ultraviolet to near infrared, and the wavelength of the light is 200-1200 nm.
6. The application of the graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds according to claim 1, wherein the volatile organic compounds are one or more of ethyl acetate, toluene or styrene.
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| CN102335592A (en) * | 2011-09-05 | 2012-02-01 | 华南理工大学 | Metal organic skeleton-graphite oxide nano composite adsorption material and preparing method thereof |
| CN103432982A (en) * | 2013-08-05 | 2013-12-11 | 华南理工大学 | Preparation method of metal organic framework-graphite oxide composite |
| CN107029673A (en) * | 2017-06-06 | 2017-08-11 | 广州星帮尼环保科技有限公司 | A kind of aluminium base MOFs/ graphene oxide composite materials and preparation method and application |
| CN113502057A (en) * | 2021-07-14 | 2021-10-15 | 华中科技大学 | Preparation method of thermal management coating based on organic metal framework composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335592A (en) * | 2011-09-05 | 2012-02-01 | 华南理工大学 | Metal organic skeleton-graphite oxide nano composite adsorption material and preparing method thereof |
| CN103432982A (en) * | 2013-08-05 | 2013-12-11 | 华南理工大学 | Preparation method of metal organic framework-graphite oxide composite |
| CN107029673A (en) * | 2017-06-06 | 2017-08-11 | 广州星帮尼环保科技有限公司 | A kind of aluminium base MOFs/ graphene oxide composite materials and preparation method and application |
| CN113502057A (en) * | 2021-07-14 | 2021-10-15 | 华中科技大学 | Preparation method of thermal management coating based on organic metal framework composite material |
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