一种茶叶渣石墨烯-CuCeMOF-PVB复合材料及其制备方法和应用Tea dregs graphene-CuCeMOF-PVB composite material and preparation method and application thereof
技术领域Technical field
本发明属于石墨烯复合材料的技术领域,特别地涉及一种茶叶渣石墨烯-CuCeMOF-PVB复合材料及其制备方法和应用。The invention belongs to the technical field of graphene composite materials, and particularly relates to a tea dregs graphene-CuCeMOF-PVB composite material and a preparation method and application thereof.
背景技术Background technique
我国茶园分布于18个省,茶区划分主要为西南、华东、江南、江北茶区,各茶区由于区域气候土地等资源的差异,所产的特色茶叶与当地的茶文化都有所差异,从而丰富了中国茶文化的内容。my country’s tea gardens are distributed in 18 provinces. The tea areas are mainly divided into Southwest, East China, Jiangnan and Jiangbei tea areas. Due to differences in regional climate, land and other resources, the characteristic tea produced in each tea area is different from the local tea culture. Thus enriching the content of Chinese tea culture.
我国盛产茶叶,其产量和出口量与日俱增,加之国家对种植业的重视,就茶叶产量而言,从2000年至2010年这十年之间,其产量从68.33万吨增至147.506万吨,至2015年,我国茶叶产量达到209.2万吨,出口量仅为30.15万吨,约占产量14.3%。由此见我国内销总量及茶叶废弃量之大。若将茶叶渣回收利用,用于制备石墨烯,不仅有利于环境的保护,也能对新材料产业提供新的产品。my country is rich in tea, and its output and export volume are increasing day by day. In addition, the country attaches great importance to the planting industry. In terms of tea output, from 2000 to 2010, its output increased from 683,300 tons to 1,475,066 tons. In 2015, my country's tea production reached 2.092 million tons, and the export volume was only 305,000 tons, accounting for approximately 14.3% of the output. This shows that the total amount of domestic sales in my country and the amount of discarded tea are large. If the tea dregs are recycled and used to prepare graphene, it will not only benefit the environment, but also provide new products for the new material industry.
现有技术中专利CN201710196300.5公开了一种CeMOF光催化材料及其制备方法与应用,联吡啶二羧酸的CeMOFs通常具有优异的光学性能,但其湿稳定性较差。Patent CN201710196300.5 in the prior art discloses a CeMOF photocatalytic material and its preparation method and application. CeMOFs of dipyridinedicarboxylic acid generally have excellent optical properties, but their wet stability is poor.
市场上使用的石墨烯导热膜和防腐涂料,尤其是有机高分子材料作为导热膜都不具备宽光谱吸收-低发射功能。因此,目前市场上还没有导热膜和防腐涂料具备宽光谱吸收-低发射功能的产品。Graphene thermally conductive films and anticorrosive coatings used in the market, especially organic polymer materials as thermally conductive films, do not have broad spectrum absorption-low emission functions. Therefore, there are no products with broad-spectrum absorption-low emission functions for thermally conductive films and anticorrosive coatings on the market.
发明内容Summary of the invention
针对以上现有技术存在的问题,本发明的目的在于提供一种茶叶渣石墨烯-CuCeMOF-PVB复合材料及其制备方法和应用,生产工艺过程安全环保、成本低且容易操作,制得的茶叶渣石墨烯-CuCeMOF-PVB复合材料具有宽光谱吸收、低发射作用。In view of the above problems in the prior art, the purpose of the present invention is to provide a tea dregs graphene-CuCeMOF-PVB composite material and its preparation method and application, the production process is safe and environmentally friendly, low cost and easy to operate, the prepared tea The slag graphene-CuCeMOF-PVB composite material has broad spectrum absorption and low emission.
本发明的技术内容如下:The technical content of the present invention is as follows:
一种茶叶渣石墨烯-CuCeMOF-PVB复合材料,其采用原料包括废弃物茶叶渣、CeMOF以及铜源物质制得的茶叶渣石墨烯-CuCeMOF-OVB复合材料,复合材料具有宽光谱吸收、低发射的功能。A kind of tea dregs graphene-CuCeMOF-PVB composite material, which adopts the tea dregs graphene-CuCeMOF-OVB composite material prepared by using raw materials including waste tea dregs, CeMOF and copper source materials. The composite material has broad spectrum absorption and low emission Function.
本发明还提供了一种茶叶渣石墨烯-CuCeMOF-PVB复合材料的制备方法,包括如下步骤:The present invention also provides a method for preparing the tea dregs graphene-CuCeMOF-PVB composite material, which includes the following steps:
1)准备PVB乙醇浆料;1) Prepare PVB ethanol slurry;
2)制备茶叶渣石墨烯:取茶叶渣干粉在氮气条件下(在氮气速率为10ml/min)升温进行加热反应,然后冷却得到茶叶渣炭,加入CH
3COOK混匀,在氮气条件下升温进行加热反应,之后冷却得到茶叶渣石墨烯;
2) Preparation of graphene of tea dregs: Take the dry powder of tea dregs and heat it up under nitrogen (at a nitrogen rate of 10ml/min) for heating reaction, and then cool to obtain tea dregs charcoal, add CH 3 COOK to mix, and perform heating under nitrogen conditions Heating reaction and then cooling to obtain graphene of tea dregs;
3)制备茶叶渣石墨烯-CuCeMOF复合物:取CeMOF、茶叶渣石墨烯以及铜源物质充分混匀,之后进行离心、洗涤,CeMOF由淡黄色变成了灰蓝色,加入DMAC、DMSO以及葡萄糖,升温进行加热反应,降至室温之后将产物进行洗涤、离心、干燥即得茶叶渣石墨烯-CuCeMOF复合物;3) Preparation of tea residue graphene-CuCeMOF composite: Take CeMOF, tea residue graphene and copper source material and mix thoroughly, then centrifuge and wash, CeMOF changes from light yellow to gray blue, add DMAC, DMSO and glucose , The temperature is raised to perform a heating reaction, and the product is washed, centrifuged, and dried to obtain the tea dregs graphene-CuCeMOF composite after being cooled to room temperature;
4)制备茶叶渣石墨烯-CuCeMOF-PVB复合材料:将PVB乙醇 浆料与茶叶渣石墨烯-CuCeMOF复合物充分混合即得茶叶渣石墨烯-CuCeMOF-PVB复合材料。4) Preparation of the tea residue graphene-CuCeMOF-PVB composite material: the PVB ethanol slurry and the tea residue graphene-CuCeMOF composite are fully mixed to obtain the tea residue graphene-CuCeMOF-PVB composite material.
其中,步骤1)所述的PVB乙醇浆料为PVB与乙醇的混合物,PVB与乙醇的使用比例为1:10~40;Wherein, the PVB ethanol slurry described in step 1) is a mixture of PVB and ethanol, and the ratio of PVB to ethanol is 1:10-40;
步骤4)所述的PVB乙醇浆料与茶叶渣石墨烯-CuCeMOF复合物的使用比例为1:1~10;Step 4) The usage ratio of the PVB ethanol slurry and the tea dregs graphene-CuCeMOF composite is 1:1-10;
步骤2)所述升温之后均保温1~5小时;Step 2) After the temperature is raised, the temperature is kept for 1 to 5 hours;
步骤3)所述的铜源物质包括乙酸铜;Step 3) The copper source material includes copper acetate;
步骤3)所述的加热反应的温度为110~140℃,保温12~24小时;Step 3) The temperature of the heating reaction is 110-140°C, and the temperature is kept for 12-24 hours;
步骤3)所述的CeMOF的制备如下:取CeCl
3·7H
2O与2,2’-联吡啶-5,5’-二甲酸混合,并加入DMF和DMSO中,室温下用玻璃棒搅拌均匀后,升温进行加热反应,之后冷却得到淡黄色析出物,进行洗涤、离心、干燥之后即得CeMOF。
Step 3) The preparation of CeMOF is as follows: Take CeCl 3 ·7H 2 O and 2,2'-bipyridine-5,5'-dicarboxylic acid, mix them, add DMF and DMSO, and stir evenly with a glass rod at room temperature After that, the temperature is raised to perform heating reaction, and then it is cooled to obtain a light yellow precipitate, which is washed, centrifuged, and dried to obtain CeMOF.
本发明还提供了一种茶叶渣石墨烯-CuCeMOF-PVB复合材料可应用于制备导热材料以及防腐涂料。The invention also provides a tea dregs graphene-CuCeMOF-PVB composite material which can be applied to the preparation of thermal conductive materials and anticorrosive coatings.
本发明的有益效果如下:The beneficial effects of the present invention are as follows:
本发明的茶叶渣石墨烯-CuCeMOF-PVB复合材料采用废弃物茶叶渣作为原料,成本低且原料普遍,解决了废弃物茶叶渣作为垃圾处理浪费资源的问题,该复合材料同时具备宽光谱吸收、低发射的功能,还具有导热作用,可用于制备导热材料(包括导热膜)和防腐涂料,导热膜可用于电子器件导热,解决了现有技术中存在的石墨烯复合材料含有对环境有害的重金属元素,且不具备宽光谱吸收、低发射的功 能等的问题;The tea dregs graphene-CuCeMOF-PVB composite material of the present invention uses waste tea dregs as raw materials, has low cost and universal raw materials, and solves the problem of waste tea dregs as garbage disposal waste resources. The composite material also has broad spectrum absorption, Low-emission function and thermal conductivity. It can be used to prepare thermal conductive materials (including thermal conductive films) and anti-corrosion coatings. Thermal conductive films can be used to conduct heat in electronic devices. This solves the problem that graphene composite materials in the prior art contain heavy metals that are harmful to the environment. Elements, and do not have the problems of broad spectrum absorption and low emission functions;
本发明的复合材料的制备工艺简单,价格低廉,安全环保,适于连续化工业生产,扩大了其应用领域,能够用于国防事业,具有广阔的市场应用前景。The composite material of the present invention has simple preparation process, low price, safety and environmental protection, is suitable for continuous industrial production, expands its application field, can be used for national defense, and has broad market application prospects.
说明书附图Description and drawings
图1为实施例1所得茶叶渣石墨烯的拉曼图谱;FIG. 1 is a Raman spectrum of the tea dregs graphene obtained in Example 1;
图2为茶叶渣石墨烯-CuCeMOF-PVB复合材料的宽光谱吸收图谱;Figure 2 shows the broad spectrum absorption spectrum of the tea dregs graphene-CuCeMOF-PVB composite material;
图3为茶叶渣石墨烯-CuCeMOF-PVB复合材料的低发射图谱。Figure 3 shows the low emission spectrum of the tea dregs graphene-CuCeMOF-PVB composite material.
具体实施方式Detailed ways
以下通过具体的实施案例以及附图说明对本发明作进一步详细的描述,应理解这些实施例仅用于说明本发明而不用于限制本发明的保护范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。The following describes the present invention in further detail through specific implementation cases and the accompanying drawings. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the protection scope of the present invention. After reading the present invention, those skilled in the art Modifications to various equivalent forms of the present invention fall within the scope of the appended claims of this application.
若无特殊说明,本发明的所有原料和试剂均为常规市场的原料、试剂。Unless otherwise specified, all the raw materials and reagents of the present invention are those in the conventional market.
实施例1Example 1
一种茶叶渣石墨烯-CuCeMOF-PVB复合材料的制备:Preparation of a tea dregs graphene-CuCeMOF-PVB composite material:
1)准备PVB乙醇浆料:将PVB粉末溶于乙醇中,形成PVB乙醇浆料;1) Prepare PVB ethanol slurry: Dissolve PVB powder in ethanol to form PVB ethanol slurry;
2)制备茶叶渣石墨烯:取茶叶渣干粉在氮气条件下(在氮气速率为10ml/min)下,以1℃/min的速率从室温升温至500~850℃, 保留1-5小时,以充分分解因燃烧产生的二噁英和除去杂原子,然后以5℃/min的速率冷却到室温,得到茶叶渣炭;2) Preparation of graphene of tea dregs: Take the dry powder of tea dregs under nitrogen conditions (at a nitrogen rate of 10ml/min), heat up from room temperature to 500-850℃ at a rate of 1℃/min, and keep it for 1-5 hours. Fully decompose the dioxins produced by combustion and remove heteroatoms, and then cool to room temperature at a rate of 5°C/min to obtain tea residue charcoal;
加入CH
3COOK(减少对炉膛的腐蚀作用,和减少生产过程中的酸和碱的用量)与茶叶渣炭研磨均匀,在氮气条件下以1℃/min的速率从室温升温至900~1150℃,保留1~5小时,进一步除去杂原子以利石墨烯的形成,然后以5℃/min的速率冷却到室温,得到茶叶渣石墨烯;
Add CH 3 COOK (to reduce the corrosive effect on the furnace, and reduce the amount of acid and alkali in the production process) and the tea pomace charcoal to grind uniformly, and heat up from room temperature to 900~1150℃ at a rate of 1℃/min under nitrogen. , Keep it for 1 to 5 hours, further remove heteroatoms to facilitate the formation of graphene, and then cool to room temperature at a rate of 5°C/min to obtain graphene of tea dregs;
3)制备茶叶渣石墨烯-CuCeMOF复合物:取CeCl
3·7H
2O,2,2’-联吡啶-5,5’-二甲酸加入到100mL的聚四氟乙烯内衬水热反应釜中,依次加入DMF和DMSO混合溶剂中,室温下用玻璃棒搅拌均匀后,将聚四氟乙烯内衬水热反应釜转移至烘箱内,3h升温至110~140℃,保温9~18h,降温速率为3℃/h,降至室温,得到淡黄色析出物,分别依次用DMF洗涤离心两次,二氯乙烷浸泡8~12h,离心分离;置于真空干燥箱中设定干燥温度80~90℃,干燥12~24h获得CeMOF;
3) Preparation of tea dregs graphene-CuCeMOF composite: take CeCl 3 ·7H 2 O, 2,2'-bipyridine-5,5'-dicarboxylic acid and add it to a 100mL PTFE-lined hydrothermal reactor , Add DMF and DMSO mixed solvent in turn, stir evenly with a glass rod at room temperature, transfer the PTFE lined hydrothermal reactor to the oven, heat up to 110~140℃ for 3h, keep it for 9~18h, and cool down The temperature is 3℃/h, down to room temperature, and light yellow precipitates are obtained, which are washed with DMF and centrifuged twice, soaked in dichloroethane for 8-12h, and centrifuged; placed in a vacuum drying oven and set the drying temperature to 80-90 ℃, dry for 12-24h to obtain CeMOF;
在获得CeMOF中添加乙酸铜和茶叶渣石墨烯,充分搅拌12h,让CeMOF与Cu
2+达到吸附平衡,之后,将混合物进行离心,用DMAC溶剂进行两次洗涤,离心分离,除去配合物CeMOF表面残留的Cu
2+,此时原本为淡黄色的配合物CeMOF呈现灰蓝色;
Add copper acetate and tea dregs graphene to the CeMOF, fully stir for 12h, let CeMOF and Cu 2+ reach adsorption equilibrium, then centrifuge the mixture, wash twice with DMAC solvent, centrifuge to remove the surface of the complex CeMOF Residual Cu 2+ , at this time the originally pale yellow complex CeMOF appears grayish blue
将灰蓝色配合物CeMOF加入到DMAC与DMSO混合溶剂中,并加入摩尔量的葡萄糖,将聚四氟乙烯内胆置于不锈钢的水热反应釜中,加热温度110~140℃,保温时间12~24h,降温时间设定12h,降至室温。产物经DMAC溶剂洗涤,然后用离心机进行高速离心 (9600rmp),每次15min,重复五次,最后将产物放在真空干燥箱中设定温度80~100℃,干燥12~24h,获得茶叶渣石墨烯-CuCeMOF复合物;The gray-blue complex CeMOF was added to the mixed solvent of DMAC and DMSO, and a molar amount of glucose was added. The polytetrafluoroethylene liner was placed in a stainless steel hydrothermal reaction kettle. The heating temperature was 110~140℃, and the holding time was 12 ~24h, the cooling time is set to 12h, down to room temperature. The product is washed with DMAC solvent, and then centrifuged at a high speed (9600rpm) with a centrifuge for 15min each time, repeated five times, and finally the product is placed in a vacuum drying oven at a temperature of 80~100℃ and dried for 12~24h to obtain tea dregs Graphene-CuCeMOF composite;
4)制备茶叶渣石墨烯-CuCeMOF-PVB复合材料:将PVB乙醇浆料与茶叶渣石墨烯-CuCeMOF复合物充分混合即得茶叶渣石墨烯-CuCeMOF-PVB复合材料。4) Preparation of the tea residue graphene-CuCeMOF-PVB composite material: the PVB ethanol slurry and the tea residue graphene-CuCeMOF composite are fully mixed to obtain the tea residue graphene-CuCeMOF-PVB composite material.
如图1所示为茶叶渣石墨烯的拉曼图谱,D峰在1365cm
-1附近,G峰出现在1685cm
-1处,茶叶渣石墨烯缺陷峰,在2685cm
-1处的2D峰的出现石墨烯的堆积方式。
Figure 1 shows the Raman spectrum of the tea dregs graphene, the D peak is around 1365cm -1 , the G peak appears at 1685cm -1 , the tea dregs graphene defect peak, and the 2D peak at 2685cm -1 appears graphite The stacking method of ene.
仪器名称:显微拉曼光谱仪,型号:LabRAM Aramis生产厂家:法国H.J.Y公司。Instrument name: Raman microscope, model: LabRAM Aramis manufacturer: French H.J.Y company.
实施例2Example 2
一种茶叶渣石墨烯-CuCeMOF-PVB导热材料的制备:Preparation of a tea dregs graphene-CuCeMOF-PVB thermal conductive material:
按1:10的比例取PVB于乙醇中溶解,静置1小时;再按照1:1的比例加入茶叶渣石墨烯-CuCeMOF复合物搅拌均匀,静置1小时到没气泡为止,通风柜中铺膜,2小时后,在烘箱中烘干成膜。Dissolve PVB in ethanol at a ratio of 1:10 and let it stand for 1 hour; then add the tea dregs graphene-CuCeMOF compound at a ratio of 1:1 and stir evenly, let it stand for 1 hour until there are no bubbles, and place in a fume hood After 2 hours, the film is dried in an oven to form a film.
经测试,导热系数通过导热系数测量仪(TC3000D,西安夏溪电子科技有限公司),导热系数在5.5W/mK。After testing, the thermal conductivity passed the thermal conductivity measuring instrument (TC3000D, Xi’an Xiaxi Electronic Technology Co., Ltd.), and the thermal conductivity was 5.5W/mK.
实施例3Example 3
一种茶叶渣石墨烯-CuCeMOF-PVB导热材料的制备:Preparation of a tea dregs graphene-CuCeMOF-PVB thermal conductive material:
按1:20的比例取PVB于乙醇中溶解,静置1小时;再按照1:2的比例加入茶叶渣石墨烯-CuCeMOF复合物搅拌均匀,静置1小时到 没气泡为止。通风柜中铺膜,2小时后,在烘箱中烘干成膜;Dissolve PVB in ethanol at a ratio of 1:20 and let it stand for 1 hour; then add the tea dregs graphene-CuCeMOF compound at a ratio of 1:2 and stir evenly, and let it stand for 1 hour until there are no bubbles. Lay the film in a fume hood and dry it in an oven after 2 hours;
经测试,导热系数在5.8W/mK。After testing, the thermal conductivity is 5.8W/mK.
实施例4Example 4
一种茶叶渣石墨烯-CuCeMOF-PVB导热材料的制备:Preparation of a tea dregs graphene-CuCeMOF-PVB thermal conductive material:
按1:25的比例取PVB于乙醇中溶解,静置1小时;再按照1:5的比例加入茶叶渣石墨烯-CuCeMOF复合物搅拌均匀,静置1小时到没气泡产生为止。通风柜中铺膜,2小时后,在烘箱中烘干成膜;Dissolve PVB in ethanol at a ratio of 1:25 and let it stand for 1 hour; then add the tea dregs graphene-CuCeMOF compound at a ratio of 1:5 and stir evenly, and let it stand for 1 hour until no bubbles are generated. Lay the film in a fume hood and dry it in an oven after 2 hours;
经测试,导热系数在6.7W/mK。After testing, the thermal conductivity is 6.7W/mK.
实施例5Example 5
一种茶叶渣石墨烯-CuCeMOF-PVB导热材料的制备:Preparation of a tea dregs graphene-CuCeMOF-PVB thermal conductive material:
按1:30的比例取PVB于乙醇中溶解,静置1小时;再按照1:7的比例加入茶叶渣石墨烯-CuCeMOF复合物搅拌均匀,静置1小时到没气泡产生为止。通风柜中铺膜,2小时后,在烘箱中烘干成膜;Dissolve PVB in ethanol at a ratio of 1:30 and let it stand for 1 hour; then add the tea dregs graphene-CuCeMOF compound at a ratio of 1:7 and stir evenly, and let it stand for 1 hour until no bubbles are generated. Lay the film in a fume hood and dry it in an oven after 2 hours;
经测试,导热系数在7.1W/mK。After testing, the thermal conductivity is 7.1W/mK.
实施例6Example 6
一种茶叶渣石墨烯-CuCeMOF-PVB导热材料的制备:Preparation of a tea dregs graphene-CuCeMOF-PVB thermal conductive material:
按1:40的比例取PVB于乙醇中溶解,静置1小时;再按照1:10的比例加入茶叶渣石墨烯-CuCeMOF复合物搅拌均匀,静置1小时到没气泡为止。通风柜中铺膜,2小时后,在烘箱中烘干成膜;Dissolve PVB in ethanol at a ratio of 1:40 and let it stand for 1 hour; then add the tea dregs graphene-CuCeMOF compound at a ratio of 1:10 and stir evenly, and let it stand for 1 hour until there are no bubbles. Lay the film in a fume hood and dry it in an oven after 2 hours;
经测试,导热系数在7.5W/mK。After testing, the thermal conductivity is 7.5W/mK.
图2为茶叶渣石墨烯-CuCeMOF-PVB复合材料的宽光谱吸收图谱(采用日本日立紫外可见光光度计U3010,引用BaSO
4,紫外-可 见漫反射数据是在200~900纳米的光谱区域),从300nm到900nm均显示了较高的吸收,可见茶叶渣石墨烯-CuCeMOF-PVB复合材料具有宽光谱吸收的功能;
Figure 2 shows the broad spectrum absorption spectrum of the tea dregs graphene-CuCeMOF-PVB composite material (using Hitachi UV-Vis photometer U3010, citing BaSO 4 , the UV-Vis diffuse reflectance data is in the 200-900 nm spectral region) Both 300nm to 900nm show high absorption, and it can be seen that the graphene-CuCeMOF-PVB composite material of tea dregs has a broad spectrum absorption function;
图3为茶叶渣石墨烯-CuCeMOF-PVB复合材料的低发射图谱(在日立F-4500荧光分光光度计上,以450W氙灯为激发光源,在室温下进行光致发光(PL)测量),其激发光的波长为300nm或350nm,可见茶叶渣石墨烯-CuCeMOF-PVB复合材料具有低发射的功能。Figure 3 shows the low emission spectrum of the tea dregs graphene-CuCeMOF-PVB composite material (on a Hitachi F-4500 fluorescence spectrophotometer, with a 450W xenon lamp as the excitation light source, photoluminescence (PL) measurement at room temperature), which The wavelength of the excitation light is 300nm or 350nm, which shows that the graphene-CuCeMOF-PVB composite material of tea dregs has a low emission function.