CN112461907B - Application of a nano-zinc oxide and graphene oxide composite material in the electrochemical detection of dopamine - Google Patents
Application of a nano-zinc oxide and graphene oxide composite material in the electrochemical detection of dopamine Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims description 40
- 229960003638 dopamine Drugs 0.000 title claims description 20
- 238000000835 electrochemical detection Methods 0.000 title claims description 7
- 230000035945 sensitivity Effects 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000001903 differential pulse voltammetry Methods 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及电化学传感技术领域,更具体地说涉及一种纳米氧化锌与还原氧化石墨烯复合材料电化学传感器及其制备方法和应用。The invention relates to the technical field of electrochemical sensing, and more specifically relates to an electrochemical sensor made of nano-zinc oxide and reduced graphene oxide composite material and its preparation method and application.
背景技术Background technique
石墨烯是一种性能优异的二维材料,因为它独特的结构使其具备了优秀的电子传输能力。氧化锌的结构多样,热稳定性好,加上它的仿生特性和高的电子传输能力,广泛被用于生物传感。而纳米氧化锌与还原氧化石墨烯复合电极也被开发出用于检测多巴胺、抗环血酸等物质。但采用的方法多为一锅法,ZnO分散的不均匀,使得复合电极对所测物质的敏感度降低。Graphene is a two-dimensional material with excellent performance, because of its unique structure, it has excellent electron transport ability. ZnO is widely used in biosensing due to its diverse structures and good thermal stability, coupled with its biomimetic properties and high electron transport capability. The nano-zinc oxide and reduced graphene oxide composite electrode has also been developed for the detection of dopamine, ascorbic acid and other substances. However, most of the methods used are one-pot method, and the uneven dispersion of ZnO reduces the sensitivity of the composite electrode to the measured substance.
发明内容Contents of the invention
本发明克服了现有技术中的不足,提供了一种纳米氧化锌与还原氧化石墨烯复合材料及其制备方法和应用,利用以金为导电基底,以纳米氧化锌(ZnO)和氧化还原石墨烯为基础材料,在导电基底上滴加两者的混合悬浮液,并且对该复合电极进行电化学还原后得到电化学传感器,该传感器对多巴胺具有很高的选择性,并且敏感度提高明显;更重要的是本方法采用电化学还原,而不是使用水热法,操作步骤简单。The present invention overcomes the deficiencies in the prior art, and provides a nano-zinc oxide and reduced graphene oxide composite material and its preparation method and application, using gold as a conductive substrate, nano-zinc oxide (ZnO) and redox graphite Alkene is used as the base material, and the mixed suspension of the two is added dropwise on the conductive substrate, and the electrochemical sensor is obtained after electrochemical reduction of the composite electrode. The sensor has high selectivity to dopamine, and the sensitivity is significantly improved; More importantly, the method adopts electrochemical reduction instead of hydrothermal method, and the operation steps are simple.
本发明的目的通过下述技术方案予以实现。The purpose of the present invention is achieved through the following technical solutions.
一种纳米氧化锌与还原氧化石墨烯复合材料及其制备方法,按照下述步骤进行:A kind of nano-zinc oxide and reduced graphene oxide composite material and preparation method thereof, carry out according to the following steps:
步骤1,对纳米氧化锌进行预处理
将纳米氧化锌颗粒超声分散于无水乙醇中,然后向上述分散液中加入3-氨丙基三乙氧基硅烷(APTES),50-90℃下水浴回流,离心洗涤干燥,得到预处理后的纳米氧化锌,其中,纳米氧化锌与3-氨丙基三乙氧基硅烷(APTES)添加质量体积比为(0.1-12):(3-60);Ultrasonically disperse nano-zinc oxide particles in absolute ethanol, then add 3-aminopropyltriethoxysilane (APTES) to the above dispersion, reflux in a water bath at 50-90°C, centrifuge, wash and dry, and obtain the pretreated Nano-zinc oxide, wherein, the mass-volume ratio of nano-zinc oxide and 3-aminopropyltriethoxysilane (APTES) is (0.1-12): (3-60);
步骤2,制备氧化还原石墨烯(GO)
将浓硫酸加入到烧杯中并加热至80-100℃,然后向上述浓硫酸中依次加入过硫酸二钾和五氧化二磷,再缓慢加入石墨粉,混合物在80-100℃下加热搅拌4-8h,冷却后,用去离子水缓慢稀释上述混合物,然后将该混合物用去离子水离心洗涤至pH=7,在室温 (20-25℃)下将得到的固体产物在空气中干燥,即得到氧化还原石墨烯(GO),其中,浓硫酸、过硫酸二钾、五氧化二磷和石墨粉的添加体积质量比为(10-50):(1-8):(3-12):(1-12);Add concentrated sulfuric acid into a beaker and heat it to 80-100°C, then add dipotassium persulfate and phosphorus pentoxide to the above concentrated sulfuric acid in sequence, then slowly add graphite powder, and heat and stir the mixture at 80-100°C for 4- 8h, after cooling, slowly dilute the above mixture with deionized water, then centrifugally wash the mixture with deionized water to pH = 7, and dry the obtained solid product in air at room temperature (20-25°C) to obtain Redox graphene (GO), wherein the added volume mass ratio of concentrated sulfuric acid, dipotassium persulfate, phosphorus pentoxide and graphite powder is (10-50): (1-8): (3-12): ( 1-12);
步骤3,制作纳米氧化锌与氧化还原石墨烯复合材料Step 3, making nano zinc oxide and redox graphene composite material
将步骤1得到的预处理后的纳米氧化锌与水配置成纳米氧化锌悬浮液,将步骤2得到的氧化还原石墨烯(GO)配置成与纳米氧化锌悬浮液等质量份的氧化还原石墨烯(GO) 悬浮液,将纳米氧化锌悬浮液与氧化还原石墨烯(GO)悬浮液搅拌混合后得到混合悬浮液,将4-10μL上述混合悬浮液滴在金电极表面,风干后得到纳米氧化锌与氧化还原石墨烯复合材料,其中,纳米氧化锌悬浮液的浓度为1-15mg/ml,氧化还原石墨烯(GO) 悬浮液的浓度为1-15mg/ml。The pretreated nano-zinc oxide and water obtained in
在步骤1中,纳米氧化锌的质量为0.2-10质量份,粒径为20-70nm,超声时间为 10-120min,APTES的体积分数为98%,体积为5-50体积份,水浴回流温度为60-80℃。In
在步骤2中,浓硫酸(H2SO4)的体积为15-40体积份,加热温度为90℃,过硫酸二钾(K2S2O4)的质量为2-7质量份,五氧化二磷(P2O5)的质量为4-10质量份,石墨粉的质量为2-10质量份。In
在步骤3中,纳米氧化锌悬浮液的浓度为1-10mg/ml,氧化还原石墨烯(GO)悬浮液的浓度为1-10mg/ml。In step 3, the concentration of the nano zinc oxide suspension is 1-10 mg/ml, and the concentration of the redox graphene (GO) suspension is 1-10 mg/ml.
其中,1质量份的含义为1g,一体积份的含义为1ml。However, one part by mass means 1 g, and one part by volume means 1 ml.
一种纳米氧化锌与还原氧化石墨烯复合材料在电化学检测多巴胺中的应用,将上述纳米氧化锌与氧化还原石墨烯复合材料置于待测溶液中进行电化学还原,电流出现向下峰值,将电流向下变化峰值进行记录,并对其进行分析后得到线性很好的浓度曲线,曲线公式为y=-0.26x-1.23,其中,y为电流峰值,x为多巴胺浓度,R2=0.998,敏感度为260nA/ μmol。An application of a nano-zinc oxide and reduced graphene oxide composite material in the electrochemical detection of dopamine. The above-mentioned nano-zinc oxide and redox graphene composite material is placed in the solution to be measured for electrochemical reduction, and the current has a downward peak value. Record the peak value of the current downward change, and analyze it to obtain a concentration curve with good linearity. The curve formula is y=-0.26x-1.23, where y is the peak value of the current, x is the concentration of dopamine, and R 2 =0.998 , with a sensitivity of 260nA/μmol.
待测溶液为多巴胺的磷酸氢二钾与磷酸二氢钾缓冲溶液(PBS),多巴胺的浓度为1-70μmol/L,电化学还原的电压为-1.2-0V,扫描速率为40-100mv/s,循环次数为15-30 圈。The solution to be tested is dipotassium hydrogen phosphate and potassium dihydrogen phosphate buffer solution (PBS) of dopamine, the concentration of dopamine is 1-70μmol/L, the voltage of electrochemical reduction is -1.2-0V, and the scanning rate is 40-100mv/s , the number of cycles is 15-30 circles.
本发明的有益效果为:本发明所制备的纳米氧化锌与还原氧化石墨烯复合材料通过对纳米氧化锌的表面进行预处理,再与所制备的氧化还原石墨烯进行搅拌混合,两者进行自组装均匀分散,使得ZnO分散更加均匀,后续利用该复合材料制备的电化学传感器,对所测物质的敏感度更高;本发明所制备的纳米氧化锌与还原氧化石墨烯复合电化学传感器,实验方法简单,实验条件易达到,有效提高了传感器电极材料的比表面积及活性位点,从而提高检测灵敏度,降低检测限,为电化学传感器的实际检测应用提供了一种新方法。The beneficial effects of the present invention are as follows: the nano-zinc oxide and reduced graphene oxide composite material prepared by the present invention pretreats the surface of the nano-zinc oxide, and then stirs and mixes with the prepared redox graphene. The assembly is evenly dispersed, so that the ZnO is more uniformly dispersed, and the subsequent electrochemical sensor prepared by using the composite material is more sensitive to the measured substance; the nano-zinc oxide and reduced graphene oxide composite electrochemical sensor prepared by the present invention, the experimental The method is simple, the experimental conditions are easy to achieve, and the specific surface area and active sites of the sensor electrode material are effectively increased, thereby improving the detection sensitivity and reducing the detection limit, and providing a new method for the actual detection application of the electrochemical sensor.
附图说明Description of drawings
图1为本发明制备的纳米氧化锌与氧化还原石墨烯复合材料的悬浮液的照片;Fig. 1 is the photo of the suspension of nano-zinc oxide prepared by the present invention and redox graphene composite material;
图2为本发明购买的纳米氧化锌的扫描电镜照片;Fig. 2 is the scanning electron micrograph of the nanometer zinc oxide that the present invention buys;
图3为本发明制备的氧化还原石墨烯的电镜照片;Fig. 3 is the electron micrograph of redox graphene prepared by the present invention;
图4为本发明制备的纳米氧化锌与氧化还原石墨烯复合材料的电镜照片;Fig. 4 is the electron micrograph of nanometer zinc oxide and redox graphene composite material prepared by the present invention;
图5为使用本发明制备的纳米氧化锌与氧化还原石墨烯复合材料在电化学工作站采用微分脉冲伏安法对不同浓度的多巴胺检测的图片,其中,(1)为DPV曲线,(2)为浓度曲线;Fig. 5 is the picture that adopts differential pulse voltammetry to detect the dopamine of different concentrations at the electrochemical workstation using the nanometer zinc oxide prepared by the present invention and redox graphene composite material, wherein, (1) is DPV curve, (2) is concentration curve;
图6为本发明制备的纳米氧化锌与氧化还原石墨烯复合材料电化学传感器电极的扫速图,其中,(1)为循环伏安曲线,(2)为电流强度曲线。Fig. 6 is a scanning speed diagram of the electrochemical sensor electrode of nano-zinc oxide and redox graphene composite material prepared by the present invention, wherein (1) is a cyclic voltammetry curve, and (2) is a current intensity curve.
具体实施方式detailed description
下面通过具体的实施例对本发明的技术方案作进一步的说明。The technical solutions of the present invention will be further described below through specific examples.
实施例1:Example 1:
将0.5g纳米氧化锌颗粒超声分散于200ml的无水乙醇中,然后加入0.5mlAPTES,在60℃下水浴回流处理4h,然后将ZnO纳米颗粒离心并用无水乙醇清洗数次后置于70℃烘箱内充分干燥,水浴回流,离心洗涤干燥,得到预处理的纳米氧化锌颗粒。Ultrasonically disperse 0.5g nano-zinc oxide particles in 200ml of absolute ethanol, then add 0.5ml of APTES, reflux in a water bath at 60°C for 4h, then centrifuge the ZnO nanoparticles and wash them with absolute ethanol several times and place them in an oven at 70°C Fully dry inside, reflux in a water bath, centrifuge, wash and dry to obtain pretreated nanometer zinc oxide particles.
将25ml浓硫酸加入到250ml烧杯中,并加热到90℃。然后依次加入5gK2S2O8和5gP2O5,再缓慢加入5g石墨粉。混合物在90℃下加热搅拌5h。冷却后,用去离子水缓慢稀释混合物。然后将该混合物使用去离子水洗涤至PH=7左右,得到的产物在室温下干燥。Add 25ml of concentrated sulfuric acid into a 250ml beaker and heat to 90°C. Then add 5g K 2 S 2 O 8 and 5g P 2 O 5 in sequence, and then slowly add 5g graphite powder. The mixture was heated and stirred at 90 °C for 5 h. After cooling, the mixture was slowly diluted with deionized water. The mixture was then washed with deionized water to around pH=7, and the resulting product was dried at room temperature.
将上述所得到的纳米氧化锌颗粒与氧化还原石墨烯分别与水配制成5mg/ml的悬浮液,搅拌混合,得到如图1所示的悬浮液,将6μL上述混合悬浮液滴在金电极表面,风干后得到纳米氧化锌与氧化还原石墨烯复合材料。Prepare the nano-zinc oxide particles and redox graphene obtained above into a 5 mg/ml suspension with water, stir and mix to obtain the suspension as shown in Figure 1, drop 6 μL of the above-mentioned mixed suspension on the surface of the gold electrode and air-dried to obtain a composite material of nano-zinc oxide and redox graphene.
通过扫描电子显微镜(SEM)对实施例1中的纳米氧化锌形貌扫描,发现纳米氧化锌的粒径为10-40nm,如图2所示。Scanning the morphology of the nano-zinc oxide in Example 1 through a scanning electron microscope (SEM), it is found that the particle size of the nano-zinc oxide is 10-40 nm, as shown in FIG. 2 .
通过扫描电子显微镜(SEM)对实施例1中制备的氧化还原石墨烯扫描,发现该氧化还原石墨烯为薄层状,如图3所示。The redox graphene prepared in Example 1 was scanned by a scanning electron microscope (SEM), and it was found that the redox graphene was in a thin layer, as shown in FIG. 3 .
如图4所示,通过扫描电子显微镜扫描发现纳米氧化锌均匀的分散在石墨烯表面。As shown in Figure 4, it was found that the nano-ZnO was uniformly dispersed on the graphene surface by scanning electron microscopy.
实施例2:Example 2:
将1g纳米氧化锌颗粒超声分散于250ml的无水乙醇中,然后加入1mlAPTES,在60℃下水浴回流处理4h,然后将ZnO纳米颗粒离心并用无水乙醇清洗数次后置于70℃烘箱内充分干燥,水浴回流,离心洗涤干燥,得到预处理的纳米氧化锌颗粒。Ultrasonic disperse 1g of zinc oxide nanoparticles in 250ml of absolute ethanol, then add 1ml of APTES, reflux in a water bath at 60°C for 4h, then centrifuge the ZnO nanoparticles and wash them with absolute ethanol several times, then place them in an oven at 70°C drying, reflux in a water bath, centrifugal washing and drying to obtain pretreated nanometer zinc oxide particles.
将20ml浓硫酸加入到250ml烧杯中,并加热到80℃。然后依次加入2.5gK2S2O8和2.5gP2O5,再缓慢加入5g石墨粉。混合物在80℃下加热搅拌5h。冷却后,用去离子水缓慢稀释混合物。然后将该混合物使用去离子水洗涤至PH=7左右,得到的产物在室温下干燥。Add 20ml of concentrated sulfuric acid into a 250ml beaker and heat to 80°C. Then add 2.5g K 2 S 2 O 8 and 2.5g P 2 O 5 in sequence, and then slowly add 5g of graphite powder. The mixture was heated and stirred at 80 °C for 5 h. After cooling, the mixture was slowly diluted with deionized water. The mixture was then washed with deionized water to around pH=7, and the resulting product was dried at room temperature.
将上述所得到的纳米氧化锌颗粒与氧化还原石墨烯分别与水配制成3mg/ml的悬浮液,搅拌混合得到悬浮液,将4μL上述混合悬浮液滴在金电极表面,风干后得到纳米氧化锌与氧化还原石墨烯复合材料。Prepare the nano-zinc oxide particles and redox graphene obtained above with water to form a suspension of 3 mg/ml, stir and mix to obtain a suspension, drop 4 μL of the above-mentioned mixed suspension on the surface of the gold electrode, and air-dry to obtain nano-zinc oxide Composites with redox graphene.
实施例3:Example 3:
将2.5g纳米氧化锌颗粒超声分散于200ml的无水乙醇中,然后加入5mlAPTES,在60℃下水浴回流处理4h,然后将ZnO纳米颗粒离心并用无水乙醇清洗数次后置于70℃烘箱内充分干燥,水浴回流,离心洗涤干燥,得到预处理的纳米氧化锌颗粒。Ultrasonically disperse 2.5g nano-zinc oxide particles in 200ml of absolute ethanol, then add 5ml of APTES, reflux in a water bath at 60°C for 4h, then centrifuge the ZnO nanoparticles and wash them with absolute ethanol for several times, then place them in an oven at 70°C Fully dry, reflux in a water bath, centrifuge, wash and dry to obtain pretreated nanometer zinc oxide particles.
将25ml浓硫酸加入到250ml烧杯中,并加热到100℃。然后依次加入5gK2S2O8和5gP2O5,再缓慢加入5g石墨粉。混合物在100℃下加热搅拌5h。冷却后,用去离子水缓慢稀释混合物。然后将该混合物使用去离子水洗涤至PH=7左右,得到的产物在室温下干燥。Add 25ml of concentrated sulfuric acid into a 250ml beaker and heat to 100°C. Then add 5g K 2 S 2 O 8 and 5g P 2 O 5 in sequence, and then slowly add 5g graphite powder. The mixture was heated and stirred at 100 °C for 5 h. After cooling, the mixture was slowly diluted with deionized water. The mixture was then washed with deionized water to around pH=7, and the resulting product was dried at room temperature.
将上述所得到的纳米氧化锌颗粒与氧化还原石墨烯分别与水配制成5mg/ml的悬浮液,搅拌混合得到悬浮液,将10μL上述混合悬浮液滴在金电极表面,风干后得到纳米氧化锌与氧化还原石墨烯复合材料。The nano-zinc oxide particles and redox graphene obtained above were formulated with water to form a 5 mg/ml suspension, stirred and mixed to obtain a suspension, 10 μL of the above-mentioned mixed suspension was dropped on the surface of the gold electrode, and the nano-zinc oxide was obtained after air-drying Composites with redox graphene.
实施例3:Example 3:
将0.1g纳米氧化锌颗粒超声分散于200ml的无水乙醇中,然后加入3mlAPTES,在60℃下水浴回流处理4h,然后将ZnO纳米颗粒离心并用无水乙醇清洗数次后置于70℃烘箱内充分干燥,水浴回流,离心洗涤干燥,得到预处理的纳米氧化锌颗粒。Ultrasonically disperse 0.1g nano-zinc oxide particles in 200ml of absolute ethanol, then add 3ml of APTES, reflux in a water bath at 60°C for 4h, then centrifuge the ZnO nanoparticles and wash them with absolute ethanol several times, then place them in an oven at 70°C Fully dry, reflux in a water bath, centrifuge, wash and dry to obtain pretreated nanometer zinc oxide particles.
将20ml浓硫酸加入到250ml烧杯中,并加热到95℃。然后依次加入1gK2S2O8和3gP2O5,再缓慢加入1g石墨粉。混合物在95℃下加热搅拌5h。冷却后,用去离子水缓慢稀释混合物。然后将该混合物使用去离子水洗涤至PH=7左右,得到的产物在室温下干燥。Add 20ml of concentrated sulfuric acid into a 250ml beaker and heat to 95°C. Then add 1g K 2 S 2 O 8 and 3g P 2 O 5 in sequence, and then slowly add 1g of graphite powder. The mixture was heated and stirred at 95 °C for 5 h. After cooling, the mixture was slowly diluted with deionized water. The mixture was then washed with deionized water to around pH=7, and the resulting product was dried at room temperature.
将上述所得到的纳米氧化锌颗粒与氧化还原石墨烯分别与水配制成15mg/ml的悬浮液,搅拌混合得到悬浮液,将9μL上述混合悬浮液滴在金电极表面,风干后得到纳米氧化锌与氧化还原石墨烯复合材料。The nano-zinc oxide particles and redox graphene obtained above were formulated with water to form a 15 mg/ml suspension, stirred and mixed to obtain a suspension, 9 μL of the above-mentioned mixed suspension was dropped on the surface of the gold electrode, and the nano-zinc oxide was obtained after air-drying Composites with redox graphene.
实施例4:Example 4:
将12g纳米氧化锌颗粒超声分散于200ml的无水乙醇中,然后加入3mlAPTES,在 60℃下水浴回流处理4h,然后将ZnO纳米颗粒离心并用无水乙醇清洗数次后置于50℃烘箱内充分干燥,水浴回流,离心洗涤干燥,得到预处理的纳米氧化锌颗粒。Ultrasonically disperse 12g nanometer zinc oxide particles in 200ml of absolute ethanol, then add 3ml of APTES, reflux in a water bath at 60°C for 4h, then centrifuge the ZnO nanoparticles and wash them with absolute ethanol several times, then place them in an oven at 50°C drying, reflux in a water bath, centrifugal washing and drying to obtain pretreated nanometer zinc oxide particles.
将50ml浓硫酸加入到250ml烧杯中,并加热到85℃。然后依次加入8gK2S2O8和12gP2O5,再缓慢加入12g石墨粉。混合物在90℃下加热搅拌5h。冷却后,用去离子水缓慢稀释混合物。然后将该混合物使用去离子水洗涤至PH=7左右,得到的产物在室温下干燥。Add 50ml of concentrated sulfuric acid into a 250ml beaker and heat to 85°C. Then add 8g K 2 S 2 O 8 and 12g P 2 O 5 in sequence, and then slowly add 12g graphite powder. The mixture was heated and stirred at 90 °C for 5 h. After cooling, the mixture was slowly diluted with deionized water. The mixture was then washed with deionized water to around pH=7, and the resulting product was dried at room temperature.
将上述所得到的纳米氧化锌颗粒与氧化还原石墨烯分别与水配制成1mg/ml的悬浮液,搅拌混合得到悬浮液,将8μL上述混合悬浮液滴在金电极表面,风干后得到纳米氧化锌与氧化还原石墨烯复合材料。Prepare the nano-zinc oxide particles and redox graphene obtained above with water to form a suspension of 1 mg/ml, stir and mix to obtain a suspension, drop 8 μL of the above-mentioned mixed suspension on the surface of the gold electrode, and air-dry to obtain nano-zinc oxide Composites with redox graphene.
实施例5:Example 5:
将实施例3中最终得到纳米氧化锌与氧化还原石墨烯复合材料置于缓冲溶液中进行电化学还原,电化学还原的电压为-1.5-0V,扫描速率为30-120mv/s,循环次数为10-40圈后,即得到纳米氧化锌与还原氧化石墨烯复合材料电化学传感器。采用三电极测试体系对样品进行电化学还原与测试,使用电化学工作站CHI-660E进行电化学还原与测试。The nano-zinc oxide and redox graphene composite material finally obtained in Example 3 is placed in a buffer solution for electrochemical reduction, the voltage of electrochemical reduction is-1.5-0V, the scan rate is 30-120mv/s, and the number of cycles is After 10-40 cycles, the electrochemical sensor of nano-zinc oxide and reduced graphene oxide composite material is obtained. The three-electrode test system was used for electrochemical reduction and testing of the samples, and the electrochemical workstation CHI-660E was used for electrochemical reduction and testing.
(1)将干燥后的电极在PBS溶液(PH=7)中进行电化学还原:电压范围为:-1.2~0V,扫描速率为50mv/s,循环次数为15次。(1) Perform electrochemical reduction on the dried electrode in PBS solution (PH=7): the voltage range is: -1.2-0V, the scan rate is 50mv/s, and the number of cycles is 15 times.
(2)将(1)中的得到的还原后的电极采用差分脉冲伏安法进行电化学测试:将此电极置于PBS缓冲液进行差分脉冲伏安法测试峰电流,电压范围为0~0.5V,扫描速率为100mv/s,脉冲周期为0.05s-1。待测物质为多巴胺,多巴胺浓度范围为1~70μmol/L,具体浓度为5 10 15 20 25 30 35 40 45 50 60 70μmol/L,最终得到DPV曲线,如图5(1)所示,在电压为0.15±0.01V时,电流出现向下峰值,经过分析可得到线性很好的浓度曲线如图5(2)所示,y=-0.26x-1.23,其中,y为电流峰值,x为多巴胺浓度,R2=0.998,敏感度为260nA/μmol。(2) Perform electrochemical test on the reduced electrode obtained in (1) by differential pulse voltammetry: put the electrode in PBS buffer solution to test the peak current by differential pulse voltammetry, and the voltage range is 0 to 0.5 V, the scan rate is 100mv/s, and the pulse period is 0.05s -1 . The substance to be tested is dopamine, and the dopamine concentration ranges from 1 to 70 μmol/L, and the specific concentration is 5 10 15 20 25 30 35 40 45 50 60 70 μmol/L. Finally, the DPV curve is obtained, as shown in Figure 5(1). When it is 0.15±0.01V, the current has a downward peak value, and after analysis, a well-linear concentration curve can be obtained as shown in Figure 5(2), y=-0.26x-1.23, wherein, y is the current peak value, and x is dopamine Concentration, R 2 =0.998, sensitivity 260 nA/μmol.
(3)将(1)中的得到的还原后的的电极进行扫速电化学测试,将此电极置于PBS 缓冲液进行循环伏安法测试峰电流,电压范围为-0.2-0.6V,扫描速率为20 40 60 80 100mv/s。得到如图6(1)所示的循环伏安曲线,且扫速与电流强度线性很好如图6(2) 所示。(3) The reduced electrode obtained in (1) is subjected to a scanning electrochemical test, and the electrode is placed in PBS buffer solution for cyclic voltammetry to test the peak current, the voltage range is -0.2-0.6V, and the scanning The rate is 20 40 60 80 100mv/s. The cyclic voltammetry curve shown in Figure 6(1) was obtained, and the linearity of the scan rate and current intensity was very good, as shown in Figure 6(2).
以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明的核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been described as an example above, and it should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be made by those skilled in the art without creative labor all fall within the scope of this invention. protection scope of the invention.
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