技术领域Technical Field
本发明属于大气光催化材料技术领域，更具体地，涉及一种氧化石墨烯/金属有机骨架复合材料在光控脱附挥发性有机物中的应用。The present invention belongs to the technical field of atmospheric photocatalytic materials, and more specifically, relates to an application of a graphene oxide/metal organic framework composite material in light-controlled desorption of volatile organic compounds.
背景技术Background technique
近年来，随着大气环境质量变差，各种环境污染事件频出，人们对大气污染的重视程度逐渐增加，作为其中一种重要的大气污染源——挥发性有机物(VOCs)也逐渐成为环境研究的热点。VOCs是导致城市灰霾和光化学烟雾的重要前提物，主要来源于煤、石油化工、燃料燃烧等过程，大多数的VOCs具有毒性、刺激性、致畸致癌性。因此，如何能够高效处理VOCs，改善环境质量成为科研人员的研究重点。VOCs的常用处理方法包括吸附、吸收、催化氧化法和生物法，其中，吸附法具有操作简单、高效、环保的特点，可应用于高、低浓度VOCs的处理。然而，工业上常用的吸附剂(活性炭、硅胶和分子筛等等)存在吸附量小、脱附较困难，吸附剂难以循环使用的问题。In recent years, with the deterioration of atmospheric environmental quality and the frequent occurrence of various environmental pollution incidents, people have gradually paid more attention to atmospheric pollution. As one of the important sources of atmospheric pollution, volatile organic compounds (VOCs) have gradually become a hot topic in environmental research. VOCs are important precursors for urban haze and photochemical smog, mainly derived from coal, petrochemicals, fuel combustion and other processes. Most VOCs are toxic, irritating, teratogenic and carcinogenic. Therefore, how to efficiently treat VOCs and improve environmental quality has become the focus of research by scientific researchers. Common treatment methods for VOCs include adsorption, absorption, catalytic oxidation and biological methods. Among them, the adsorption method has the characteristics of simple operation, high efficiency and environmental protection, and can be applied to the treatment of high and low concentrations of VOCs. However, the adsorbents commonly used in industry (activated carbon, silica gel and molecular sieves, etc.) have the problems of small adsorption capacity, difficult desorption and difficult recycling of adsorbents.
金属有机骨架材料(MOFs)是一种由无机二级建筑单元(金属氧化物团簇或金属离子)与有机组分配位组成的有机-无机多孔材料，这种配位聚合物提供了显著的化学和结构多样性，由于孔径可调、表面可进行修饰等特点，其在分子水平上吸附有害气体/蒸汽方面优于传统的多孔材料，在吸附去除VOCs的应用案例也很多。但由于MOF自身较差的热传导性，致使最常用的热脱附技术脱附VOCs时面临率较低、能耗高。氧化石墨烯(GO)在可见光和近红外(NIR)电磁波谱中表现出广泛的光学吸收和优异的光热转换性能，广泛应用于癌症治疗、海水纯化等方面，但是氧化石墨烯是单层网状结构，比表面积和孔隙率均较低，在吸附高浓度VOCs方面应用收到限制。截止目前，对光热转换应用于吸脱附VOCs的研究尚少。Metal-organic frameworks (MOFs) are organic-inorganic porous materials composed of inorganic secondary building units (metal oxide clusters or metal ions) coordinated with organic components. This coordination polymer provides significant chemical and structural diversity. Due to the characteristics of adjustable pore size and surface modification, it is superior to traditional porous materials in adsorbing harmful gases/vapors at the molecular level, and there are many application cases in the adsorption and removal of VOCs. However, due to the poor thermal conductivity of MOF itself, the most commonly used thermal desorption technology faces low efficiency and high energy consumption when desorbing VOCs. Graphene oxide (GO) exhibits a wide range of optical absorption and excellent photothermal conversion performance in the visible and near-infrared (NIR) electromagnetic spectra, and is widely used in cancer treatment, seawater purification, etc. However, graphene oxide is a single-layer mesh structure with low specific surface area and porosity, which limits its application in the adsorption of high-concentration VOCs. Up to now, there is little research on the application of photothermal conversion in the adsorption and desorption of VOCs.
发明内容Summary of the invention
为了解决现有常用的VOCs吸附剂吸附容量小、太阳能利用率低、脱附效率低和脱附耗能高等不足，本发明首要目的在于提供了一种氧化石墨烯/金属有机骨架复合材料在光控脱附挥发性有机物中的应用。该材料具有较高光热转换性能，能够结合氧化石墨烯的光热转换性能和MOF的多孔吸附特点，可在太阳光的驱动下改善材料的再生性能，解决了太阳能利用率低、MOF脱附效率低的缺陷，拓展了MOF在VOCs处理方面的应用前景。In order to solve the shortcomings of existing commonly used VOCs adsorbents, such as small adsorption capacity, low solar energy utilization, low desorption efficiency and high desorption energy consumption, the primary purpose of the present invention is to provide a graphene oxide/metal organic framework composite material for light-controlled desorption of volatile organic compounds. The material has high photothermal conversion performance, can combine the photothermal conversion performance of graphene oxide and the porous adsorption characteristics of MOF, can improve the regeneration performance of the material under the drive of sunlight, solve the defects of low solar energy utilization and low MOF desorption efficiency, and expand the application prospects of MOF in VOCs treatment.
本发明的目的通过下述技术方案来实现：The purpose of the present invention is achieved through the following technical solutions:
一种氧化石墨烯/金属有机骨架复合材料在光控脱附挥发性有机物中的应用，所述复合材料氧化石墨烯/金属有机骨架复合材料，简写为GO/MIL-101，是将氧化石墨烯超声分散于水中，形成GO悬浮液；再将GO悬浮液和Cr盐加入到带聚四氟乙烯的反应釜中搅拌均匀后，加入有机配体对苯二甲酸和水，升温至160～220℃水热反应6～16h，洗涤、干燥制得。The invention discloses an application of a graphene oxide/metal organic framework composite material in light-controlled desorption of volatile organic compounds. The composite material, graphene oxide/metal organic framework composite material, abbreviated as GO/MIL-101, is prepared by ultrasonically dispersing graphene oxide in water to form a GO suspension; then adding the GO suspension and Cr salt into a reactor with polytetrafluoroethylene and stirring evenly, adding organic ligand terephthalic acid and water, heating to 160-220°C for hydrothermal reaction for 6-16h, washing and drying.
优选地，所述的氧化石墨烯为单层片状，其尺寸为500nm～1μm。Preferably, the graphene oxide is in the form of a single-layer sheet with a size of 500 nm to 1 μm.
优选地，所述Cr盐为CrCl3·6H2O或Cr(NO3)3·9H2O；所述Cr盐、对苯二甲酸和水的摩尔比为1：(1～2)：(500～600)；所述GO悬浮液中氧化石墨烯和Cr盐的摩尔比为(0.02～0.1)：1。所述的GO悬浮液的浓度为2～4mg/mL。Preferably, the Cr salt is CrCl3 ·6H2 O or Cr(NO3 )3 ·9H2 O; the molar ratio of the Cr salt, terephthalic acid and water is 1:(1-2):(500-600); the molar ratio of graphene oxide and Cr salt in the GO suspension is (0.02-0.1):1. The concentration of the GO suspension is 2-4 mg/mL.
优选地，所述升温的速率为0.1～1℃/min；所述干燥的温度为80～120℃，干燥的时间为12～20h。Preferably, the heating rate is 0.1-1°C/min; the drying temperature is 80-120°C, and the drying time is 12-20h.
优选地，所述光为从紫外到近红外光区，所述光的波长为200～1200nm。Preferably, the light is in the ultraviolet to near infrared region, and the wavelength of the light is 200 to 1200 nm.
优选地，所述挥发性有机物为乙酸乙酯、甲苯或苯乙烯。Preferably, the volatile organic compound is ethyl acetate, toluene or styrene.
本发明氧化石墨烯/金属有机骨架复合材料能够实现光控VOCs吸脱附的机理是：氧化石墨烯物理性质可调、环境相容性高，且能够吸收可见光和近红外区的光谱，具有全光谱的光吸收性能，金属有机骨架材料具有较大的比表面积和孔体积，能够用于吸附富集VOCs，但是通常金属有机骨架材料的光吸收范围较窄。光热转化性能较弱。因此，将氧化石墨烯和金属有机骨架材料结合，氧化石墨烯先与金属源发生配位，有效地提高了光能利用率和复合材料的再生性能，既能吸附大量的VOCs，又能提高光热转化性能进而脱附VOCs，实现了对VOCs的高效处理。The mechanism by which the graphene oxide/metal organic framework composite material of the present invention can achieve light-controlled VOCs adsorption and desorption is: graphene oxide has adjustable physical properties, high environmental compatibility, and can absorb the spectrum of visible light and near-infrared regions, and has full-spectrum light absorption performance. Metal organic framework materials have a large specific surface area and pore volume, and can be used to adsorb and enrich VOCs, but metal organic framework materials generally have a narrow light absorption range. The photothermal conversion performance is relatively weak. Therefore, graphene oxide and metal organic framework materials are combined, and graphene oxide first coordinates with the metal source, which effectively improves the light energy utilization rate and the regeneration performance of the composite material, and can not only adsorb a large amount of VOCs, but also improve the photothermal conversion performance and then desorb VOCs, thereby achieving efficient treatment of VOCs.
将氧化石墨烯/金属有机骨架复合材料应用于吸脱附处理VOCs，氧化石墨烯覆盖在MOF表面，氧化石墨烯的网状蜂窝结构对MOF的比表面积影响较小，对于吸附过程影响较小。GO具有优异的光吸收性能和热传导性能，与MOF复合后，该复合材料不仅保留MOF大的吸附容量，且能够拓宽并增强MOF的光吸收范围和强度，在200～1200nm波长的光照射下，能够吸收大量的光能并转化成热能，由于MOF生长在GO表面，致使GO产生的大量热能经历较短的距离传输到MOF表面，激发被吸附VOCs的快速脱附，实现吸附剂的高效、快速再生。该光控吸附技术可避免传统外源加热的长距离热传输，有效地克服了MOF热传导性差的问题。The graphene oxide/metal organic framework composite material is applied to the adsorption and desorption of VOCs. The graphene oxide covers the surface of MOF. The mesh honeycomb structure of graphene oxide has little effect on the specific surface area of MOF and has little effect on the adsorption process. GO has excellent light absorption and thermal conductivity. After compounding with MOF, the composite material not only retains the large adsorption capacity of MOF, but also can broaden and enhance the light absorption range and intensity of MOF. Under the irradiation of light with a wavelength of 200 to 1200nm, it can absorb a large amount of light energy and convert it into heat energy. Since MOF grows on the surface of GO, the large amount of heat energy generated by GO is transmitted to the surface of MOF over a short distance, stimulating the rapid desorption of adsorbed VOCs, and realizing efficient and rapid regeneration of the adsorbent. This light-controlled adsorption technology can avoid the long-distance heat transmission of traditional external heating, and effectively overcome the problem of poor thermal conductivity of MOF.
与现有的技术对比，本发明有以下的优势：Compared with the existing technology, the present invention has the following advantages:
1.本发明的复合材料不仅保留MOF大的吸附容量，且能够拓宽并增强MOF的光吸收范围和强度。因此，在太阳光照射下能够吸收大量的光能并转化成热能，激发VOCs的快速脱附，实现吸附剂的再生。单层片状氧化石墨烯具有物理性质可调节、环境相容性较高，而且在水溶液中不易聚集和堆积，有利于MOF在其表面的均匀生长；在可见光和近红外区光谱吸收性能好，在太阳光的驱动下，能够有效地将光能转化为热能并传递给MOF，高效地利用了太阳能。1. The composite material of the present invention not only retains the large adsorption capacity of MOF, but also can broaden and enhance the light absorption range and intensity of MOF. Therefore, under the irradiation of sunlight, it can absorb a large amount of light energy and convert it into heat energy, stimulate the rapid desorption of VOCs, and realize the regeneration of the adsorbent. The single-layer flaky graphene oxide has adjustable physical properties and high environmental compatibility, and is not easy to aggregate and accumulate in aqueous solution, which is conducive to the uniform growth of MOF on its surface; it has good spectral absorption performance in the visible light and near-infrared regions, and under the drive of sunlight, it can effectively convert light energy into heat energy and transfer it to MOF, making efficient use of solar energy.
2.本发明采用水热法合成氧化石墨烯/金属有机骨架复合材料，条件温和，通过氧化石墨烯和Cr盐的充分搅拌，氧化石墨烯表面的羧基官能团可与Cr3+优先配位，之后加入有机配体，能够有效地将MOF附着在氧化石墨烯表面，拓宽了MOF的光吸收范围，有效地将太阳光转化成热量传递到MOF，实现材料的再生。2. The present invention adopts a hydrothermal method to synthesize graphene oxide/metal organic framework composite materials under mild conditions. Through sufficient stirring of graphene oxide and Cr salt, the carboxyl functional groups on the surface of graphene oxide can preferentially coordinate with Cr3+ . After that, the addition of organic ligands can effectively attach MOF to the surface of graphene oxide, broaden the light absorption range of MOF, effectively convert sunlight into heat and transfer it to MOF, and realize the regeneration of the material.
3.本发明的GO/MIL-101对VOCs(如乙酸乙酯)具有良好的吸附和脱附性能。对中高浓度(200～2000ppm)的挥发性有机物(如乙酸乙酯)，GO/MIL-101在太阳光的驱动下，在30min内脱附VOCs(如乙酸乙酯)达90％以上。3. The GO/MIL-101 of the present invention has good adsorption and desorption performance for VOCs (such as ethyl acetate). For medium and high concentrations (200-2000ppm) of volatile organic compounds (such as ethyl acetate), GO/MIL-101 desorbs more than 90% of VOCs (such as ethyl acetate) within 30 minutes under the drive of sunlight.
4.本发明与升温脱附、降压脱附、吹扫脱附等传统的脱附技术相比，该氧化石墨烯/金属有机骨架复合材料应用在光控脱附挥发性有机物中具有工艺简单、脱附速度快、能耗低等优点，适合于工业化生产，应用前景广阔。4. Compared with traditional desorption technologies such as temperature desorption, pressure reduction desorption, and purge desorption, the graphene oxide/metal organic framework composite material used in the photo-controlled desorption of volatile organic compounds has the advantages of simple process, fast desorption speed, low energy consumption, etc., is suitable for industrial production, and has broad application prospects.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1所得GO/MIL-101在波长200-1200nm光照下的光热转换性能。FIG1 shows the photothermal conversion performance of GO/MIL-101 obtained in Example 1 under light with a wavelength of 200-1200 nm.
图2为实施例1所得GO/MIL-101对乙酸乙酯气体的吸脱附曲线图。FIG. 2 is a graph showing the adsorption and desorption curves of ethyl acetate gas on GO/MIL-101 obtained in Example 1.
具体实施方式Detailed ways
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The content of the present invention is further described below in conjunction with specific examples, but it should not be construed as limiting the present invention. If not specifically indicated, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.
实施例1Example 1
1.复合材料的制备1. Preparation of composite materials
(1)称量30mg的GO超声6h分散于10mL水中，形成3mg/mL的GO悬浮液；(1) Weigh 30 mg of GO and disperse it in 10 mL of water by ultrasonication for 6 h to form a 3 mg/mL GO suspension;
(2)取上述5mL的GO悬浮液和CrCl3·6H2O加入到反应釜中并搅拌混合1h，再按照CrCl3·6H2O：C8H6O4：水＝1:1:500的摩尔比(即称量0.4622g CrCl3·6H2O、0.2853g C8H6O4和10mL水)加入到高压反应釜中，以1℃/min的速率升至190℃水热反应16h，自然冷却至室温，用DMF和水分别抽滤三次，100℃真空干燥12h，得到氧化石墨烯/金属有机骨架复合材料，简写为GO/MIL-101；其中，GO为GO/MIL-101的2mol％。(2) 5 mL of the GO suspension and CrCl3 ·6H2 O were added to a reactor and stirred for 1 h. Then, the mixture was added to a high-pressure reactor in a molar ratio of CrCl3 ·6H2 O:C8 H6 O4 :water=1:1:500 (i.e., 0.4622 g CrCl3 ·6H2 O, 0.2853 g C8 H6 O4 and 10 mL water). The mixture was heated to 190°C at a rate of 1°C/min for hydrothermal reaction for 16 h. The mixture was naturally cooled to room temperature, filtered with DMF and water three times respectively, and dried in vacuo at 100°C for 12 h to obtain a graphene oxide/metal organic framework composite material, abbreviated as GO/MIL-101. GO was 2 mol% of GO/MIL-101.
2.性能测试2. Performance Testing
将GO/MIL-101复合材料涂至样品反应器表面，并用氙灯模拟太阳光照，使用红外照相机分别记录下在紫外-可见光和紫外-近红外光谱区照射下，材料表面温度变化。图1为本实施例所得GO/MIL-101在太阳光照(200-1200nm)光热转换性能。从图1可以看出，本发明的GO/MIL-101可在120s内温度升高至120℃以上。说明氧化石墨烯能够协助MOF发挥更好的光热传导效应。图2为实施例1所得GO/MIL-101对乙酸乙酯气体的吸脱附曲线图。从图2可以看出，GO/MIL-101可在30min内脱附乙酸乙酯达90％以上。结果表明，GO/MIL-101复合材料能够提高纯MOF的光热转换性能，有助于实现MOF的高效、快速再生。The GO/MIL-101 composite material was applied to the surface of the sample reactor, and a xenon lamp was used to simulate sunlight. An infrared camera was used to record the changes in the surface temperature of the material under irradiation in the ultraviolet-visible light and ultraviolet-near infrared spectral regions. Figure 1 shows the photothermal conversion performance of GO/MIL-101 obtained in this embodiment under sunlight (200-1200nm). As can be seen from Figure 1, the temperature of GO/MIL-101 of the present invention can be increased to above 120°C within 120s. This shows that graphene oxide can assist MOF in exerting a better photothermal conduction effect. Figure 2 is a graph of the adsorption and desorption curve of ethyl acetate gas by GO/MIL-101 obtained in Example 1. As can be seen from Figure 2, GO/MIL-101 can desorb more than 90% of ethyl acetate within 30min. The results show that the GO/MIL-101 composite material can improve the photothermal conversion performance of pure MOF and help to achieve efficient and rapid regeneration of MOF.
实施例2Example 2
1.称量30mg的GO超声6h分散于10mL水中，形成3mg/mL的GO悬浮液；1. Weigh 30 mg of GO and disperse it in 10 mL of water by ultrasonic for 6 h to form a 3 mg/mL GO suspension;
2.取上述10mL的GO悬浮液和CrCl3·6H2O加入到反应釜中并搅拌混合1h，再按照CrCl3·6H2O：C8H6O4：水＝1:1:500的摩尔比(即称量0.3806g CrCl3·6H2O、0.2649g C8H6O4和10mL水)加入到高压反应釜中，以1℃/min的速率升至190℃水热反应16h，自然冷却至室温，用DMF和水分别抽滤三次，100℃真空干燥12h，得到氧化石墨烯/金属有机骨架复合材料，简写为GO/MIL-101。其中，GO为GO/MIL-101的5mol％。2. Take 10 mL of the above GO suspension and CrCl3 ·6H2 O and add them to the reactor and stir and mix for 1 hour, then add them to the autoclave according to the molar ratio of CrCl3 ·6H2 O: C8 H6 O4 : water = 1:1:500 (i.e. weigh 0.3806 g CrCl3 ·6H2 O, 0.2649 g C8 H6 O4 and 10 mL water), heat to 190°C at a rate of 1°C/min for hydrothermal reaction for 16 hours, cool naturally to room temperature, filter with DMF and water three times respectively, and vacuum dry at 100°C for 12 hours to obtain graphene oxide/metal organic framework composite material, abbreviated as GO/MIL-101. Among them, GO is 5 mol% of GO/MIL-101.
将GO/MIL-101复合材料涂至样品反应器表面，并用氙灯模拟太阳光照，使用红外照相机分别记录下在紫外-可见光和紫外-近红外光谱区照射下，材料表面温度变化。该复合材料分别在150s和120s表面温度升高至88℃和137℃。说明氧化石墨烯能够协助MOF发挥更好的光热传导效应。The GO/MIL-101 composite material was coated on the surface of the sample reactor, and a xenon lamp was used to simulate sunlight. The surface temperature changes of the material were recorded using an infrared camera under the irradiation of the UV-visible light and UV-near infrared spectral regions. The surface temperature of the composite material rose to 88°C and 137°C in 150s and 120s, respectively. This shows that graphene oxide can help MOF to achieve better photothermal conductivity.
实施例3Example 3
1.称量60mg的GO超声6h分散于20mL水中，形成3mg/mL的GO悬浮液；1. Weigh 60 mg of GO and disperse it in 20 mL of water by ultrasonic for 6 h to form a 3 mg/mL GO suspension;
2.取上述15mL的GO(0.04g)悬浮液和CrCl3·6H2O加入到反应釜中并搅拌混合1h，再按照CrCl3·H2O：C8H6O4：水＝1:1:500的摩尔比(即称量0.3263gCrCl3·6H2O、0.2014gC8H6O4和10mL水)加入到高压反应釜中，以1℃/min的速率升至190℃水热反应16h，自然冷却至室温，用DMF和水分别抽滤三次，100℃真空干燥12h，得到氧化石墨烯/金属有机骨架复合材料，简写为GO/MIL-101。其中，GO为GO/MIL-101复合材料的10mol％。2. Take 15 mL of the above GO (0.04 g) suspension and CrCl3 ·6H2 O and add them to the reactor and stir for 1 hour, then add them to the autoclave according to the molar ratio of CrCl3 ·H2 O:C8 H6 O4 :water=1:1:500 (i.e. weigh 0.3263 g CrCl3 ·6H2 O, 0.2014 g C8 H6 O4 and 10 mL water), heat to 190°C at a rate of 1°C/min for hydrothermal reaction for 16 hours, cool naturally to room temperature, filter with DMF and water three times respectively, and vacuum dry at 100°C for 12 hours to obtain graphene oxide/metal organic framework composite material, abbreviated as GO/MIL-101. Among them, GO is 10 mol% of the GO/MIL-101 composite material.
将GO/MIL-101复合材料涂至样品反应器表面，并用氙灯模拟太阳光照，使用红外照相机分别记录下在紫外-可见光和紫外-近红外光谱区照射下，材料表面温度变化。该复合材料分别在100s和80s表面温度升高至73℃和136℃。说明氧化石墨烯能够协助MOF发挥更好的光热传导效应。The GO/MIL-101 composite material was coated on the surface of the sample reactor, and a xenon lamp was used to simulate sunlight. The surface temperature changes of the material were recorded using an infrared camera under the irradiation of the UV-visible light and UV-near infrared spectral regions. The surface temperature of the composite material increased to 73°C and 136°C in 100s and 80s, respectively. This shows that graphene oxide can help MOF to achieve better photothermal conductivity.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
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| CN103432982A (en)* | 2013-08-05 | 2013-12-11 | 华南理工大学 | Preparation method of metal organic framework-graphite oxide composite |
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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 |
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| 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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