技术领域Technical field
本申请涉及传感器领域，特别涉及一种基于垂直石墨烯微电极阵列的电化学传感装置及制备方法。The present application relates to the field of sensors, and in particular to an electrochemical sensing device based on a vertical graphene microelectrode array and a preparation method.
背景技术Background technique
生物体内的代谢物参数的测量通常生物传感器检测或电化学传感器检测。生物传感是指利用固定化的生物敏感材料作识别元件来检测外界环境中的物质或能量，并将检测结果转换成电信号或其他便于处理的信号。生物化学检测是利用生物体内的化学反应来检测生物体的状态，如血液检测、尿液检测等。作为传感器技术领域的一个新分支，电化学生物传感器通过生物与电子检测技术的结合，对生物体内的生理参数进行定量测量。电化学传感器不仅可以用于检测氧化还原反应，如氧化还原电位、氧化还原电流、氧化还原电容等电化学参数，还可以用于检测电解质的浓度，如氯化物、硫酸根、氢离子等。The measurement of metabolite parameters in living organisms is usually done by biosensor detection or electrochemical sensor detection. Biosensing refers to the use of immobilized biologically sensitive materials as identification elements to detect substances or energy in the external environment, and convert the detection results into electrical signals or other signals that are easy to process. Biochemical testing uses chemical reactions in organisms to detect the status of organisms, such as blood tests, urine tests, etc. As a new branch in the field of sensor technology, electrochemical biosensors quantitatively measure physiological parameters in organisms through the combination of biological and electronic detection technologies. Electrochemical sensors can not only be used to detect redox reactions, such as redox potential, redox current, redox capacitance and other electrochemical parameters, but can also be used to detect the concentration of electrolytes, such as chloride, sulfate, hydrogen ions, etc.
相关技术中，电化学传感主要分为酶传感以及离子传感两大类，同样也存在使用分子印迹聚合物等多种方式，使用石墨烯作为传感材料提高了酶传感器的耐久度以及稳定性，但对于微型化的传感器，由于传感面积的限制，石墨烯传感器所采集到信号电流较小，并不能满足良好的传感性能。现有的传感器以单个参数的测量为主，不能同时测量多个参数；或者是多参数传感器的集成基本是单个类别传感器的集成，如传感器中均为酶传感器或者均为离子传感器，检测方式单一。另外，通过安培-时间测试法对待测溶液进行检测，但该方法会生成氧化还原电流，对电极检测造成一定的干扰，长时间连续测试会对工作电极造成负担，导致电极传感精度降低。因此，现有的电化学传感器在测量复杂疾病等场景应用中受到了一定限制。In related technologies, electrochemical sensing is mainly divided into two categories: enzyme sensing and ion sensing. There are also various methods such as the use of molecularly imprinted polymers. The use of graphene as a sensing material improves the durability of enzyme sensors and However, for miniaturized sensors, due to the limitation of the sensing area, the signal current collected by the graphene sensor is small and cannot meet good sensing performance. Existing sensors mainly measure a single parameter and cannot measure multiple parameters at the same time; or the integration of multi-parameter sensors is basically the integration of a single category of sensors. For example, the sensors are all enzyme sensors or all ion sensors, and the detection method is single. . In addition, the solution to be tested is detected through the ampere-time test method, but this method will generate a redox current, which will cause certain interference to the electrode detection. Long-term continuous testing will burden the working electrode, resulting in a reduction in electrode sensing accuracy. Therefore, existing electrochemical sensors are subject to certain limitations in applications such as measuring complex diseases.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
本申请旨在至少解决现有技术中存在的技术问题之一。为此，本申请实施例提供了一种基于垂直石墨烯微电极阵列的电化学传感装置及制备方法，有利于解决电化学传感器传感功能单一且传感检测效率低下的问题。本申请设置电化学传感器由垂直石墨烯微传感电极阵列、对电极和参比电极组成，并设置电化学工作站与化学传感器连接，通过差分脉冲伏安法实时检测待测溶液中多种代谢物的浓度，微传感电极阵列能够同时对待测溶液进行多种代谢物浓度的检测，提高了传感器的检测效率，同时适配多参数的检测场景；通过使用差分脉冲伏安法进行检测，避免产生杂质电流，提高了电化学传感器的检测精度。This application aims to solve at least one of the technical problems existing in the prior art. To this end, embodiments of the present application provide an electrochemical sensing device and a preparation method based on a vertical graphene microelectrode array, which is beneficial to solving the problems of single sensing function and low sensing detection efficiency of electrochemical sensors. This application sets up an electrochemical sensor consisting of a vertical graphene micro-sensing electrode array, a counter electrode and a reference electrode, and sets up an electrochemical workstation connected to the chemical sensor to detect multiple metabolites in the solution to be measured in real time through differential pulse voltammetry. The micro-sensing electrode array can detect the concentration of multiple metabolites in the solution to be measured at the same time, which improves the detection efficiency of the sensor and adapts to multi-parameter detection scenarios; by using differential pulse voltammetry for detection, it avoids the occurrence of Impurity current improves the detection accuracy of electrochemical sensors.
第一方面，本申请实施例提供了一种基于垂直石墨烯微电极阵列的电化学传感装置，包括电化学传感器，所述电化学传感器由垂直石墨烯微传感电极阵列、对电极和参比电极组成；电化学工作站，所述电化学工作站用于与所述化学传感器连接并通过差分脉冲伏安法实时检测待测溶液中多种代谢物的浓度。In a first aspect, embodiments of the present application provide an electrochemical sensing device based on a vertical graphene microelectrode array, including an electrochemical sensor. The electrochemical sensor is composed of a vertical graphene microsensing electrode array, a counter electrode and a parameter. It consists of a specific electrode; an electrochemical workstation, which is used to connect with the chemical sensor and detect the concentration of multiple metabolites in the solution to be measured in real time through differential pulse voltammetry.
本申请上述第一方面的技术方案至少具有如下的优点或有益效果之一：通过设置电化学传感器由垂直石墨烯微传感电极阵列、对电极和参比电极组成，微传感电极阵列能够同时对待测溶液进行多种代谢物浓度的检测，提高了传感器的检测效率，同时适配多参数的检测场景；设置化学传感器与电化学工作站连接，并通过差分脉冲伏安法实时检测待测溶液中多种代谢物的浓度，避免产生杂质电流，提高了电化学传感器的检测精度。The above-mentioned technical solution of the first aspect of the present application has at least one of the following advantages or beneficial effects: by arranging the electrochemical sensor to be composed of a vertical graphene micro-sensing electrode array, a counter electrode and a reference electrode, the micro-sensing electrode array can simultaneously Detect the concentration of multiple metabolites in the solution to be tested, which improves the detection efficiency of the sensor and adapts to multi-parameter detection scenarios; set up the chemical sensor to connect to the electrochemical workstation, and detect the solution in the solution to be tested in real time through differential pulse voltammetry The concentration of multiple metabolites avoids the generation of impurity current and improves the detection accuracy of the electrochemical sensor.
进一步，所述垂直石墨烯微传感电极阵列用于同时检测待测溶液中的多种代谢物的浓度，所述垂直石墨烯微传感电极阵列包括钠离子传感电极、钙离子传感电极、钾离子传感电极、多巴胺传感电极、抗坏血酸传感电极、尿酸传感电极中的一种或多种。Further, the vertical graphene micro-sensing electrode array is used to simultaneously detect the concentration of multiple metabolites in the solution to be measured. The vertical graphene micro-sensing electrode array includes sodium ion sensing electrodes and calcium ion sensing electrodes. , one or more of a potassium ion sensing electrode, a dopamine sensing electrode, an ascorbic acid sensing electrode, and a uric acid sensing electrode.
进一步，所述垂直石墨烯微传感电极由层叠结构组成，所述层叠结构以石墨纸基底，依次由垂直石墨烯层、铂层和酶层叠层组成。Further, the vertical graphene micro-sensing electrode is composed of a stacked structure, which is based on graphite paper and consists of a vertical graphene layer, a platinum layer and an enzyme layer stack in sequence.
进一步，所述层叠结构还包括选择性薄膜层，所述选择性薄膜层黏附于所述铂层，所述选择性薄膜的种类和所述垂直石墨烯微传感电极阵列中传感电极的种类对应。Further, the laminated structure also includes a selective film layer, the selective film layer is adhered to the platinum layer, the type of the selective film and the type of sensing electrode in the vertical graphene micro-sensing electrode array. correspond.
进一步，所述酶层包括尿酸酶、乳酸酶，胆固醇酶、葡萄糖氧化酶中的一种或多种。Further, the enzyme layer includes one or more of uricase, lactase, cholesterol enzyme, and glucose oxidase.
进一步，所述垂直石墨烯微传感电极阵列中传感电极的直径为1.7毫米。Further, the diameter of the sensing electrodes in the vertical graphene micro-sensing electrode array is 1.7 mm.
第二方面，本申请实施例提供了一种基于垂直石墨烯微电极阵列的电化学传感装置的制备方法，所述电化学传感装置包括电化学传感器，所述电化学传感器的制备方法包括：In a second aspect, embodiments of the present application provide a method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array. The electrochemical sensing device includes an electrochemical sensor. The preparation method of the electrochemical sensor includes: :
以石墨纸为基底材料，通过射频辅助的等离子体增强化学气相沉积法对所述石墨纸进行预处理，得到沉积的垂直石墨烯；Using graphite paper as a base material, the graphite paper is pretreated through a radio frequency-assisted plasma enhanced chemical vapor deposition method to obtain deposited vertical graphene;
将带有垂直石墨烯的石墨纸放置在磁控溅射仪器中溅射铂层，得到初级垂直石墨烯传感电极；Place the graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode;
在预设数量的所述初级垂直石墨烯传感器上均匀滴涂用于检测不同代谢物对应的酶层和选择性薄膜，得到垂直石墨烯微传感电极阵列；Apply enzyme layers and selective films corresponding to different metabolites evenly on a preset number of primary vertical graphene sensors to obtain a vertical graphene micro-sensing electrode array;
将通过乙醇超声清洁的聚酰亚胺作为基底材料放进预设的磁控溅射仪中进行金层沉积预处理，得到初级对电极；Put the polyimide ultrasonically cleaned with ethanol as the base material into a preset magnetron sputtering instrument for gold layer deposition pretreatment to obtain a primary counter electrode;
将所述初级对电极滴涂配置好的聚氨酯溶液，并静置第一预设时间，得到对电极；Drop-coat the prepared polyurethane solution on the primary counter electrode and let it stand for a first preset time to obtain a counter electrode;
将经过磁控溅射金层的聚酰亚胺浸入设置有预设浓度的银电镀液中进行电镀，得到初级参比电极；The polyimide that has undergone magnetron sputtering gold layer is immersed in a silver electroplating solution with a preset concentration for electroplating to obtain a primary reference electrode;
对所述初级参比电极使用聚乙烯醇缩丁醛的甲醇溶液进行浸没涂覆，并放置在室温下晾干，得到参比电极；The primary reference electrode is immersed in a methanol solution of polyvinyl butyral and left to dry at room temperature to obtain a reference electrode;
将所述垂直石墨烯微传感电极阵列、所述对电极、所述参比电极分别贴附于预设的聚酰亚胺基底上进行固定，得到电化学传感器。The vertical graphene micro-sensing electrode array, the counter electrode, and the reference electrode are respectively attached to a preset polyimide substrate and fixed to obtain an electrochemical sensor.
本申请上述第二方面的技术方案至少具有如下的优点或有益效果之一：采用等离子体增强化学气相沉积法对石墨纸进行预处理，得到垂直石墨烯，以垂直石墨烯为基底依次磁控溅射铂层、并均匀滴涂对应的催化酶以及选择性膜，得到垂直石墨烯传感电极，制备流程简单，结构稳定；垂直石墨烯微比传统的石墨烯传感材料更大的比表面积，为酶层叠层的催化酶提供了良好的接触位点，从而提高了垂直石墨烯微传感电极的灵敏度和响应能力。将垂直石墨烯微传感电极阵列、对电极、参比电极分别贴附于预设的聚酰亚胺基底上进行固定，得到电化学传感器。将制备而成的电化学传感器配合差分脉冲伏安法检测待测溶液中多种代谢物的浓度，使得垂直石墨烯材料进一步在微传感电极阵列上采集到更大的信号强度，同时保证了酶传感器的使用寿命，提高了电化学传感器的机械性能以及检测精度。The above-mentioned second aspect of the technical solution of the present application has at least one of the following advantages or beneficial effects: using plasma-enhanced chemical vapor deposition method to pretreat graphite paper to obtain vertical graphene, and sequentially magnetron sputtering using the vertical graphene as the base The platinum layer is sprayed, and the corresponding catalytic enzyme and selective membrane are evenly coated to obtain a vertical graphene sensing electrode. The preparation process is simple and the structure is stable; the vertical graphene micro has a larger specific surface area than traditional graphene sensing materials. It provides good contact sites for the catalytic enzymes in the enzyme layer stack, thereby improving the sensitivity and responsiveness of the vertical graphene micro-sensing electrodes. The vertical graphene micro-sensing electrode array, counter electrode, and reference electrode are respectively attached to the preset polyimide substrate and fixed to obtain an electrochemical sensor. The prepared electrochemical sensor is used with differential pulse voltammetry to detect the concentration of various metabolites in the solution to be measured, allowing the vertical graphene material to further collect greater signal intensity on the micro-sensing electrode array, while ensuring The service life of the enzyme sensor improves the mechanical performance and detection accuracy of the electrochemical sensor.
进一步，在所述将经过磁控溅射金层的聚酰亚胺浸入设置有预设浓度的银电镀液中进行电镀，得到初级参比电极之后，所述方法还包括：Further, after the polyimide that has undergone the magnetron sputtering gold layer is immersed in a silver electroplating solution with a preset concentration for electroplating to obtain a primary reference electrode, the method also includes:
将所述初级参比电极放入去离子水溶液中刷洗、取出并自然烘干；Put the primary reference electrode into a deionized water solution, brush it, take it out and dry it naturally;
使用氯化银油墨对自然烘干的所述初级参比电极进行涂覆，并放置于烘箱中以第一预设温度进行烘干。The naturally dried primary reference electrode is coated with silver chloride ink, and placed in an oven to dry at a first preset temperature.
进一步，所述以石墨纸为基底材料，通过射频辅助的等离子体增强化学气相沉积法对所述石墨纸进行预处理，得到沉积的垂直石墨烯包括：Further, the graphite paper is used as the base material, and the graphite paper is pretreated by a radio frequency-assisted plasma enhanced chemical vapor deposition method to obtain deposited vertical graphene including:
以石墨纸为基底材料，对所述石墨纸以第一预设射频功率、预设的气体总质量流量和预设的气体压力进行沉积处理，Using graphite paper as the base material, the graphite paper is deposited with a first preset radio frequency power, a preset total gas mass flow rate, and a preset gas pressure,
在所述沉积处理过程中，采用在氢气中预设体积浓度的甲烷气体作为碳源，并使基板温度保持在预设的温度区间，持续第二预设时间对所述石墨纸进行沉积处理，得到沉积的垂直石墨烯。During the deposition process, methane gas with a preset volume concentration in hydrogen is used as a carbon source, the substrate temperature is maintained at a preset temperature range, and the graphite paper is deposited for a second preset time, Deposited vertical graphene was obtained.
进一步，所述将带有垂直石墨烯的石墨纸放置在磁控溅射仪器中溅射铂层，得到初级垂直石墨烯传感电极包括：Further, placing the graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode includes:
将带有垂直石墨烯的石墨纸放置于GVC-2000磁控溅射仪中，装配铂靶并连接氩气和氮气进行抽真空保持第三预设时间的磁控溅射。Place the graphite paper with vertical graphene in the GVC-2000 magnetron sputtering instrument, assemble the platinum target and connect the argon and nitrogen gases for magnetron sputtering that is evacuated and maintained for a third preset time.
本申请的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本申请而了解。本申请的目的和其他优点可通过在说明书、权利要求书以及附图中所特别指出的结构来实现和获得。Additional features and advantages of the application will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the application. The objectives and other advantages of the application may be realized and obtained by the structure particularly pointed out in the specification, claims and appended drawings.
附图说明Description of the drawings
图1是本申请实施例提供的一种基于垂直石墨烯微电极阵列的电化学传感装置的结构示意图；Figure 1 is a schematic structural diagram of an electrochemical sensing device based on a vertical graphene microelectrode array provided by an embodiment of the present application;
图2是本申请实施例提供的电化学传感器的结构示意图；Figure 2 is a schematic structural diagram of an electrochemical sensor provided by an embodiment of the present application;
图3是本申请实施例提供的叠层结构的示意图；Figure 3 is a schematic diagram of a stacked structure provided by an embodiment of the present application;
图4是本申请实施例提供的基于垂直石墨烯微电极阵列的电化学传感装置中的电化学传感器的制备方法；Figure 4 is a method for preparing an electrochemical sensor in an electrochemical sensing device based on a vertical graphene microelectrode array provided by an embodiment of the present application;
图5是本申请实施例提供的另一种基于垂直石墨烯微电极阵列的电化学传感装置中的电化学传感器的制备方法；Figure 5 is another method for preparing an electrochemical sensor in an electrochemical sensing device based on a vertical graphene microelectrode array provided by an embodiment of the present application;
图6是图4中S100的步骤流程图；Figure 6 is a step flow chart of S100 in Figure 4;
图7是本申请实施例提供的一种垂直石墨烯的表面传感区域的扫描电镜表征图；Figure 7 is a scanning electron microscope characterization diagram of the surface sensing area of vertical graphene provided by the embodiment of the present application;
图8是本申请实施例提供的一种垂直石墨烯经过磁控溅射铂层的传感区域的扫描电镜表征图。FIG. 8 is a scanning electron microscope characterization diagram of the sensing area of vertical graphene passing through a magnetron sputtered platinum layer according to an embodiment of the present application.
具体实施方式Detailed ways
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。In order to make the purpose, technical solutions and advantages of the present application more clear, the present application will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.
在本申请的描述中，多个指的是两个以上。如果有描述到第一、第二只是用于区分技术特征为目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量或者隐含指明所指示的技术特征的先后关系。In the description of this application, multiple refers to two or more. If there is a description of first and second, it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying the relative importance or implicitly indicating the number of indicated technical features or implicitly indicating the order of indicated technical features. relation.
相关技术中，电化学传感主要分为酶传感以及离子传感两大类，同样也存在使用分子印迹聚合物等多种方式，使用石墨烯作为传感材料提高了酶传感器的耐久度以及稳定性，但对于微型化的传感器，由于传感面积的限制，石墨烯传感器所采集到信号电流较小，并不能满足良好的传感性能。常见的工作电极包括金属电极、汞电极、碳电极等。由于待检测环境试样中存在活性物质的干扰，电化学传感器长期使用稳定性差，目标分析物选择性差、灵敏度低，因此，如何进一步提高传感器的灵敏度、稳定性和选择性是当前电化学传感器应用于环境检测领域亟需解决的重要问题。In related technologies, electrochemical sensing is mainly divided into two categories: enzyme sensing and ion sensing. There are also various methods such as the use of molecularly imprinted polymers. The use of graphene as a sensing material improves the durability of enzyme sensors and However, for miniaturized sensors, due to the limitation of the sensing area, the signal current collected by the graphene sensor is small and cannot meet good sensing performance. Common working electrodes include metal electrodes, mercury electrodes, carbon electrodes, etc. Due to the interference of active substances in the environmental samples to be detected, electrochemical sensors have poor long-term stability, poor selectivity for target analytes, and low sensitivity. Therefore, how to further improve the sensitivity, stability and selectivity of the sensor is the current application of electrochemical sensors. Important issues that need to be solved urgently in the field of environmental testing.
现有的传感器以单个参数的测量为主，不能同时测量多个参数；或者是多参数传感器的集成基本是单个类别传感器的集成，如传感器中均为酶传感器或者均为离子传感器，检测方式单一。另外，通过安培-时间测试法对待测溶液进行检测，但该方法会生成氧化还原电流，对电极检测造成一定的干扰，长时间连续测试会对工作电极造成负担，导致电极传感精度降低。因此，现有的电化学传感器在测量复杂疾病等场景应用中受到了一定限制。为此，本申请实施例提供了一种基于垂直石墨烯微电极阵列的电化学传感装置及制备方法，有利于解决电化学传感器传感功能单一且传感检测效率低下的问题。Existing sensors mainly measure a single parameter and cannot measure multiple parameters at the same time; or the integration of multi-parameter sensors is basically the integration of a single category of sensors. For example, the sensors are all enzyme sensors or all ion sensors, and the detection method is single. . In addition, the solution to be tested is detected through the ampere-time test method, but this method will generate a redox current, which will cause certain interference to the electrode detection. Long-term continuous testing will burden the working electrode, resulting in a reduction in electrode sensing accuracy. Therefore, existing electrochemical sensors are subject to certain limitations in applications such as measuring complex diseases. To this end, embodiments of the present application provide an electrochemical sensing device and a preparation method based on a vertical graphene microelectrode array, which is beneficial to solving the problems of single sensing function and low sensing detection efficiency of electrochemical sensors.
本申请实施例提供了一种基于垂直石墨烯微电极阵列的电化学传感装置，参照图1，基于垂直石墨烯微电极阵列的电化学传感装置包括电化学传感器1000和电化学工作站(图中未示)，其中，电化学传感器1000由垂直石墨烯微传感电极阵列100、对电极200和参比电极300组成。电化学工作站用于与化学传感器1000连接并通过差分脉冲伏安法实时检测待测溶液中多种代谢物的浓度。The embodiment of the present application provides an electrochemical sensing device based on a vertical graphene microelectrode array. Referring to Figure 1, the electrochemical sensing device based on a vertical graphene microelectrode array includes an electrochemical sensor 1000 and an electrochemical workstation (Fig. (not shown), in which the electrochemical sensor 1000 is composed of a vertical graphene micro-sensing electrode array 100, a counter electrode 200 and a reference electrode 300. The electrochemical workstation is used to connect to the chemical sensor 1000 and detect the concentrations of multiple metabolites in the solution to be measured in real time through differential pulse voltammetry.
通过设置电化学传感器由垂直石墨烯微传感电极阵列、对电极和参比电极组成，微传感电极阵列能够同时对待测溶液进行多种代谢物浓度的检测，提高了传感器的检测效率，同时适配多参数的检测场景；设置化学传感器与电化学工作站连接，并通过差分脉冲伏安法实时检测待测溶液中多种代谢物的浓度，避免产生杂质电流，提高了电化学传感器的检测精度。By setting up an electrochemical sensor consisting of a vertical graphene micro-sensing electrode array, a counter electrode and a reference electrode, the micro-sensing electrode array can simultaneously detect the concentration of multiple metabolites in the solution to be tested, improving the detection efficiency of the sensor. Adapt to multi-parameter detection scenarios; set up chemical sensors to connect to electrochemical workstations, and detect the concentrations of multiple metabolites in the solution to be tested in real time through differential pulse voltammetry, avoiding the generation of impurity currents and improving the detection accuracy of electrochemical sensors. .
参照图2，图2是本申请实施例提供的另一种基于垂直石墨烯微电极阵列的电化学传感装置中电化学传感器1000的结构示意图，电化学传感器1000由垂直石墨烯微传感电极阵列100、对电极200和参比电极300组成。其中，垂直石墨烯微传感电极阵列100包括钠离子传感电极10、钙离子传感电极20、钾离子传感电极30、多巴胺传感电极40、抗坏血酸传感电极50、尿酸传感电极60。Referring to Figure 2, Figure 2 is a schematic structural diagram of an electrochemical sensor 1000 in another electrochemical sensing device based on a vertical graphene microelectrode array provided by an embodiment of the present application. The electrochemical sensor 1000 is composed of vertical graphene micro-sensing electrodes. The array 100 is composed of a counter electrode 200 and a reference electrode 300. Among them, the vertical graphene micro-sensing electrode array 100 includes a sodium ion sensing electrode 10, a calcium ion sensing electrode 20, a potassium ion sensing electrode 30, a dopamine sensing electrode 40, an ascorbic acid sensing electrode 50, and a uric acid sensing electrode 60. .
垂直石墨烯微传感电极阵列100能够同时对待测溶液进行多种代谢物浓度的检测，提高了传感器的检测效率；将垂直石墨烯微传感电极阵列100和化学工作站连接，通过差分脉冲伏安法实时检测待测溶液中钠离子、钙离子、钾离子、多巴胺、抗坏血酸、尿酸的浓度，实时动态检测待测溶液中多种代谢物的浓度，适配多参数的检测场景。The vertical graphene micro-sensing electrode array 100 can detect the concentration of multiple metabolites in the solution to be measured at the same time, which improves the detection efficiency of the sensor; the vertical graphene micro-sensing electrode array 100 is connected to the chemical workstation, and through differential pulse voltammetry The method detects the concentrations of sodium ions, calcium ions, potassium ions, dopamine, ascorbic acid, and uric acid in the solution to be tested in real time, and dynamically detects the concentrations of multiple metabolites in the solution to be tested in real time, adapting to multi-parameter detection scenarios.
需要说明的是，由于差分脉冲伏安法对工作电极上施加的激励电压为呈线性增长的脉冲波，排除了由于电位随时间变化而产生的电容电流对最后测试结果的干扰，能够极大程度的减少了测试过程中由于制备不规范而产生的杂质引发的氧化还原电流。It should be noted that since the excitation voltage applied to the working electrode by differential pulse voltammetry is a pulse wave that increases linearly, it eliminates the interference of the capacitive current caused by the change of potential with time on the final test results, and can greatly improve the test results. It reduces the redox current caused by impurities caused by irregular preparation during the test process.
需要说明的是，垂直石墨烯微传感电极阵列100包括钠离子传感电极、钙离子传感电极、钾离子传感电极、多巴胺传感电极、抗坏血酸传感电极、尿酸传感电极中的一种或多种，还可以包括氨基酸传感电极、糖类传感电极、脂肪酸传感电极和维生素传感电极中的一种或多种。本申请实施例对垂直石墨烯微传感电极阵列100的传感电极的类型不作限制，可根据实际需求进行设置对应的传感电极。It should be noted that the vertical graphene micro-sensing electrode array 100 includes one of a sodium ion sensing electrode, a calcium ion sensing electrode, a potassium ion sensing electrode, a dopamine sensing electrode, an ascorbic acid sensing electrode, and a uric acid sensing electrode. One or more kinds may also include one or more of amino acid sensing electrodes, sugar sensing electrodes, fatty acid sensing electrodes and vitamin sensing electrodes. The embodiments of the present application do not limit the types of sensing electrodes of the vertical graphene micro-sensing electrode array 100, and corresponding sensing electrodes can be set according to actual needs.
需要说明的是，本申请实施例中垂直石墨烯微传感电极阵列中传感电极的直径为1.7毫米，比传统的石墨烯传感材料更大的比表面积，为酶层叠层4的催化酶提供了良好的接触位点，从而提高了垂直石墨烯微传感电极的灵敏度和响应能力。垂直石墨烯微传感电极阵列中传感电极的直径可以根据实际测试需求进行设置，本申请实施例对垂直石墨烯微传感电极阵列中传感电极的直径的大小不作限制。It should be noted that in the embodiment of the present application, the diameter of the sensing electrode in the vertical graphene micro-sensing electrode array is 1.7 mm, which has a larger specific surface area than the traditional graphene sensing material, and is the catalytic enzyme of the enzyme layer 4 Provides good contact sites, thereby improving the sensitivity and responsiveness of vertical graphene micro-sensing electrodes. The diameter of the sensing electrodes in the vertical graphene micro-sensing electrode array can be set according to actual test requirements. The embodiments of this application do not limit the size of the diameter of the sensing electrodes in the vertical graphene micro-sensing electrode array.
参照图3，图3是叠层结构的示意图，垂直石墨烯微传感电极由层叠结构组成，所述层叠结构以石墨纸基底1，依次由垂直石墨烯层2、铂层3和酶层叠层4组成。垂直石墨烯层2为比传统的石墨烯传感材料更大的比表面积，为酶层叠层4的催化酶提供了良好的接触位点，从而提高了垂直石墨烯微传感电极的灵敏度和响应能力；其次在垂直石墨烯层2上磁控溅射铂层3，对垂直石墨烯层2起到了保护作用，提高了叠层结构的稳定性，同时铂层3可以对酶层叠层4的催化酶产生的过氧化氢进行响应，提高了垂直石墨烯微传感电极的检测性能。Referring to Figure 3, Figure 3 is a schematic diagram of a stacked structure. The vertical graphene micro-sensing electrode is composed of a stacked structure. The stacked structure uses a graphite paper base 1, and is sequentially composed of a vertical graphene layer 2, a platinum layer 3 and an enzyme layer. Composed of 4. Vertical graphene layer 2 has a larger specific surface area than traditional graphene sensing materials, providing good contact sites for catalytic enzymes in enzyme layer stack 4, thereby improving the sensitivity and response of the vertical graphene micro-sensing electrode. ability; secondly, magnetron sputtering platinum layer 3 on the vertical graphene layer 2 protects the vertical graphene layer 2 and improves the stability of the stacked structure. At the same time, the platinum layer 3 can catalyze the enzyme layer stack 4 The hydrogen peroxide produced by the enzyme responds, improving the detection performance of the vertical graphene micro-sensing electrode.
本申请实施例中，层叠结构还包括选择性薄膜层(图中未示)，选择性薄膜层黏附于铂层3，选择性薄膜的种类和垂直石墨烯微传感电极阵列100中传感电极的种类对应。In the embodiment of the present application, the stacked structure also includes a selective thin film layer (not shown in the figure), the selective thin film layer is adhered to the platinum layer 3, the type of the selective thin film and the sensing electrodes in the vertical graphene micro-sensing electrode array 100 corresponding to the type.
需要说明的是，本申请实施例中选择性薄膜层包括钠离子选择膜层、钙离子选择膜层、钾离子选择膜层、多巴胺选择膜层、抗坏血酸选择膜层、尿酸选择膜层中的一种或多种，还可以包括氨基酸选择膜层、糖类选择膜层、脂肪酸选择膜层和维生素选择膜层中的一种或多种。本申请实施例对选择膜层的类型不作限制，可根据实际需求进行设置对应的选择膜层。It should be noted that in the embodiments of the present application, the selective film layer includes one of a sodium ion selective film layer, a calcium ion selective film layer, a potassium ion selective film layer, a dopamine selective film layer, an ascorbic acid selective film layer, and a uric acid selective film layer. One or more kinds, and may also include one or more of an amino acid selection film layer, a carbohydrate selection film layer, a fatty acid selection film layer and a vitamin selection film layer. The embodiments of the present application do not limit the type of the selected film layer, and the corresponding selected film layer can be set according to actual needs.
需要说明的是，酶层叠层4包括尿酸酶、乳酸酶，胆固醇酶、葡萄糖氧化酶中的一种或多种，酶层叠层4可根据实际检测需求进行设置，本申请实施例对酶层叠层4的类型不作限制。It should be noted that the enzyme layer stack 4 includes one or more of uricase, lactase, cholesterol enzyme, and glucose oxidase. The enzyme layer stack 4 can be configured according to actual detection requirements. In the embodiment of the present application, the enzyme layer stack 4 4 types are not restricted.
参照图4，图4是本申请实施例提供的一种基于垂直石墨烯微电极阵列的电化学传感装置的制备方法，其中，电化学传感装置包括电化学传感器，电化学传感器的制备方法包括步骤S100至S800，具体地，Referring to Figure 4, Figure 4 is a method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array provided by an embodiment of the present application, wherein the electrochemical sensing device includes an electrochemical sensor. A method for preparing an electrochemical sensor. Including steps S100 to S800, specifically,
S100：以石墨纸为基底材料，通过射频辅助的等离子体增强化学气相沉积法对石墨纸进行预处理，得到沉积的垂直石墨烯；S100: Using graphite paper as the base material, pretreat the graphite paper through radio frequency-assisted plasma-enhanced chemical vapor deposition method to obtain deposited vertical graphene;
S200：将带有垂直石墨烯的石墨纸放置在磁控溅射仪器中溅射铂层，得到初级垂直石墨烯传感电极；S200: Place the graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode;
S300：在预设数量的初级垂直石墨烯传感器上均匀滴涂用于检测不同代谢物对应的酶层和选择性薄膜，得到垂直石墨烯微传感电极阵列；S300: Evenly drop-coat enzyme layers and selective films for detecting different metabolites on a preset number of primary vertical graphene sensors to obtain a vertical graphene micro-sensing electrode array;
S400：将通过乙醇超声清洁的聚酰亚胺作为基底材料放进预设的磁控溅射仪中进行金层沉积预处理，得到初级对电极；S400: Put the polyimide ultrasonically cleaned with ethanol as the base material into a preset magnetron sputtering instrument for gold layer deposition pretreatment to obtain the primary counter electrode;
S500：将初级对电极滴涂配置好的聚氨酯溶液，并静置第一预设时间，得到对电极；S500: Drop-coat the prepared polyurethane solution on the primary counter electrode and let it stand for the first preset time to obtain the counter electrode;
S600：将经过磁控溅射金层的聚酰亚胺浸入设置有预设浓度的银电镀液中进行电镀，得到初级参比电极；S600: Dip the polyimide that has undergone magnetron sputtering gold layer into a silver plating solution with a preset concentration for electroplating to obtain a primary reference electrode;
S700：对初级参比电极使用聚乙烯醇缩丁醛的甲醇溶液进行浸没涂覆，并放置在室温下晾干，得到参比电极；S700: The primary reference electrode is immersed in a methanol solution of polyvinyl butyral and left to dry at room temperature to obtain a reference electrode;
S800：将垂直石墨烯微传感电极阵列、对电极、参比电极分别贴附于预设的聚酰亚胺基底上进行固定，得到电化学传感器。S800: The vertical graphene micro-sensing electrode array, counter electrode, and reference electrode are respectively attached to the preset polyimide substrate and fixed to obtain an electrochemical sensor.
本申请实施例中，采用等离子体增强化学气相沉积法对石墨纸进行预处理，得到垂直石墨烯，以垂直石墨烯为基底依次磁控溅射铂层、并均匀滴涂对应的催化酶以及选择性膜，得到垂直石墨烯传感电极，制备流程简单，结构稳定；垂直石墨烯微比传统的石墨烯传感材料更大的比表面积，为酶层叠层的催化酶提供了良好的接触位点，从而提高了垂直石墨烯微传感电极的灵敏度和响应能力。通过乙醇超声清洁的聚酰亚胺作为基底材料放进预设的磁控溅射仪中进行预处理，并滴涂配置好的聚氨酯溶液后进行精致，得到对电极。将经过磁控溅射金层的聚酰亚胺浸入设置有预设浓度的银电镀液中进行电镀，通过恒压法进行电化学沉积银处理，并使用聚乙烯醇缩丁醛的甲醇溶液进行浸没涂覆，并放置在室温下晾干，得到参比电极。最后将垂直石墨烯微传感电极阵列、对电极、参比电极分别贴附于预设的聚酰亚胺基底上进行固定，得到电化学传感器。将制备而成的电化学传感器配合差分脉冲伏安法检测待测溶液中多种代谢物的浓度，使得垂直石墨烯材料进一步在传感电极阵列上采集到更大的信号强度，同时保证了酶传感器的使用寿命，提高了电化学传感器的机械性能以及检测精度。In the embodiments of this application, the plasma-enhanced chemical vapor deposition method is used to pretreat the graphite paper to obtain vertical graphene. The vertical graphene is used as the base to sequentially magnetron sputter the platinum layer, and the corresponding catalytic enzyme and selection are evenly dripped. The vertical graphene sensing electrode is obtained by forming a vertical graphene sensing electrode with a simple preparation process and a stable structure; the vertical graphene micro has a larger specific surface area than traditional graphene sensing materials, providing a good contact site for the catalytic enzyme in the enzyme layer. , thereby improving the sensitivity and responsiveness of vertical graphene micro-sensing electrodes. The polyimide cleaned ultrasonically by ethanol was used as the base material and put into a preset magnetron sputtering instrument for pretreatment. The prepared polyurethane solution was drop-coated and polished to obtain a counter electrode. The polyimide that has undergone the magnetron sputtering gold layer is immersed in a silver electroplating solution with a preset concentration for electroplating, and electrochemical silver deposition is performed by a constant voltage method, using a methanol solution of polyvinyl butyral. Immerse the coating and leave it to dry at room temperature to obtain the reference electrode. Finally, the vertical graphene micro-sensing electrode array, counter electrode, and reference electrode were attached to the preset polyimide substrate and fixed to obtain an electrochemical sensor. The prepared electrochemical sensor is used with differential pulse voltammetry to detect the concentration of multiple metabolites in the solution to be measured, allowing the vertical graphene material to further collect greater signal intensity on the sensing electrode array, while ensuring that the enzyme The service life of the sensor improves the mechanical performance and detection accuracy of the electrochemical sensor.
需要说明的是，本申请实施例中第一预设时间为6小时至8小时，第一预设时间根据制备环境的温度根据实际要求进行设置，本申请实施例对第一预设时间不作限制。It should be noted that in the embodiment of the present application, the first preset time is 6 hours to 8 hours. The first preset time is set according to the temperature of the preparation environment according to actual requirements. The embodiment of the present application does not limit the first preset time. .
需要说明的是，将通过乙醇超声清洁的聚酰亚胺作为基底材料放进预设的磁控溅射仪中进行预处理，得到初级对电极包括使用乙醇超声清洁的聚酰亚胺作为基底材料，放入格微GVC-2000磁控溅射仪中，装配金靶并连接上氩气和氮气后进行抽真空，进行10至15分钟的磁控溅射，得到初级对电极。It should be noted that the polyimide ultrasonically cleaned with ethanol is used as the base material and put into a preset magnetron sputtering instrument for pretreatment to obtain a primary counter electrode including the polyimide ultrasonically cleaned with ethanol as the base material. , put it into the GVC-2000 magnetron sputtering instrument, assemble the gold target and connect it to argon and nitrogen, then evacuate it, and perform magnetron sputtering for 10 to 15 minutes to obtain the primary counter electrode.
参照图5，图5是本申请实施例提供的另一种基于垂直石墨烯微电极阵列的电化学传感装置的制备方法包括步骤S610至S620，具体地，Referring to Figure 5, Figure 5 illustrates another method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array provided by an embodiment of the present application, including steps S610 to S620. Specifically,
S600：将经过磁控溅射金层的聚酰亚胺浸入设置有预设浓度的银电镀液中进行电镀，得到初级参比电极；S600: Dip the polyimide that has undergone magnetron sputtering gold layer into a silver plating solution with a preset concentration for electroplating to obtain a primary reference electrode;
S610：将初级参比电极放入去离子水溶液中刷洗、取出并自然烘干；S610: Put the primary reference electrode into deionized water solution, brush it, take it out and dry it naturally;
S620：使用氯化银油墨对自然烘干的初级参比电极进行涂覆，并放置于烘箱中以第一预设温度进行烘干。S620: Use silver chloride ink to coat the naturally dried primary reference electrode, and place it in an oven to dry at the first preset temperature.
在烧杯中加入定量的银电镀液，并将经过磁控溅射金层的聚酰亚胺放入电镀液中进行电镀，并使用恒压法在电镀液中进行电化学沉积银，得到初级参比电极，沉积后放入去离子水溶液中轻轻涮洗，取出后自然烘干；然后使用银/氯化银油墨进行涂覆，并在烤箱中以第一预设温度烘干。烘干后取出后，使用聚乙烯醇缩丁醛的甲醇溶液进行浸没涂覆，在室温下晾干，得到参比电极。Add a certain amount of silver plating solution into the beaker, put the polyimide that has undergone magnetron sputtering gold layer into the plating solution for electroplating, and use the constant voltage method to electrochemically deposit silver in the plating solution to obtain the primary parameters. For the specific electrode, after deposition, put it into a deionized water solution and rinse it gently, take it out and dry it naturally; then use silver/silver chloride ink to coat it, and dry it in the oven at the first preset temperature. After drying, take it out, use a methanol solution of polyvinyl butyral for immersion coating, and dry it at room temperature to obtain a reference electrode.
需要说明的是，将经过磁控溅射金层的聚酰亚胺浸入设置有预设浓度的银电镀液中进行电镀包括使用恒压法进行电化学沉积银处理，具体地，使用2V的电压持续350s的沉积处理。It should be noted that immersing the polyimide that has undergone magnetron sputtering gold layer into a silver electroplating solution with a preset concentration for electroplating includes electrochemical silver deposition using a constant voltage method. Specifically, a voltage of 2V is used. The deposition process lasts for 350s.
需要说明的是，第一预设温度为95℃至98℃，第一预设温度可以根据制备环境按实际需求进行设置，本申请实施例对第一预设温度不作限制。It should be noted that the first preset temperature is 95°C to 98°C. The first preset temperature can be set according to actual needs according to the preparation environment. The embodiment of the present application does not limit the first preset temperature.
参照图6，图6是图1中S100的步骤流程图，包括步骤S110至S120，具体地，Referring to Figure 6, Figure 6 is a step flow chart of S100 in Figure 1, including steps S110 to S120. Specifically,
S110：以石墨纸为基底材料，对石墨纸以第一预设射频功率、预设的气体总质量流量和预设的气体压力进行沉积处理，S110: Using graphite paper as the base material, deposit the graphite paper with the first preset radio frequency power, the preset total gas mass flow rate and the preset gas pressure.
S120：在沉积处理过程中，采用在氢气中预设体积浓度的甲烷气体作为碳源，并使基板温度保持在预设的温度区间，持续第二预设时间对石墨纸进行沉积处理，得到沉积的垂直石墨烯。S120: During the deposition process, methane gas with a preset volume concentration in hydrogen is used as the carbon source, and the temperature of the substrate is maintained in the preset temperature range, and the graphite paper is deposited for a second preset time to obtain the deposition of vertical graphene.
本申请实施例中，以石墨纸为基底材料，通过射频辅助的等离子体增强化学气相沉积法对石墨纸进行预处理，得到沉积的垂直石墨烯具体包括对石墨纸以第一预设射频功率、预设的气体总质量流量和预设的气体压力进行沉积处理，并且在沉积处理过程中，采用在氢气中预设体积浓度的甲烷气体作为碳源，并使基板温度保持在预设的温度区间，持续第二预设时间对石墨纸进行沉积处理，得到沉积的垂直石墨烯。In the embodiment of the present application, graphite paper is used as the base material, and the graphite paper is preprocessed by radio frequency-assisted plasma-enhanced chemical vapor deposition. Obtaining the deposited vertical graphene specifically includes applying the first preset radio frequency power to the graphite paper, The deposition process is performed at a preset total gas mass flow rate and a preset gas pressure, and during the deposition process, a preset volume concentration of methane gas in hydrogen is used as a carbon source, and the substrate temperature is maintained in a preset temperature range. , the graphite paper is deposited for a second preset time to obtain deposited vertical graphene.
以石墨纸为基底材料，通过化学气相沉积法对石墨纸进行沉积处理得到垂直石墨烯传感电极，制备流程简单，结构稳定；垂直石墨烯微比传统的石墨烯传感材料更大的比表面积，为酶层叠层的催化酶提供了良好的接触位点，从而提高了垂直石墨烯微传感电极的灵敏度和响应能力。Using graphite paper as the base material, vertical graphene sensing electrodes are obtained by depositing graphite paper through chemical vapor deposition. The preparation process is simple and the structure is stable; vertical graphene has a larger specific surface area than traditional graphene sensing materials. , providing good contact sites for the catalytic enzymes in the enzyme layer stack, thereby improving the sensitivity and responsiveness of the vertical graphene micro-sensing electrode.
需要说明的是，本申请实施例中，在沉积过程中，第一预设射频功率为1000至2000W、预设的气体总质量流量为5至10sccm以及气体压力保持在6至12Pa。本申请实施例中第一预设射频功率、预设的气体总质量流量以及气体压力可以根据制备过程中的实际需求进行设置，本申请实施例对第一预设射频功率、预设的气体总质量流量以及气体压力的大小不作限制。It should be noted that in the embodiment of the present application, during the deposition process, the first preset radio frequency power is 1000 to 2000W, the preset total gas mass flow rate is 5 to 10 sccm, and the gas pressure is maintained at 6 to 12 Pa. In the embodiment of the present application, the first preset radio frequency power, the preset total gas mass flow rate and the gas pressure can be set according to the actual needs during the preparation process. In the embodiment of the present application, the first preset radio frequency power, the preset total gas mass flow rate and the preset gas pressure The mass flow rate and gas pressure are not limited.
需要说明的是，本申请实施例中，在沉积过程中，预设的温度区间为600℃至900℃，第二预设时间为5至40分钟，通过采用在氢气中体积浓度为5％至100％的甲烷气体作为碳源，同时使基板温度在600℃至900℃之间变化，进行持续5分钟至40分钟进行垂直石墨烯的沉积，从而制备出垂直石墨烯。It should be noted that in the embodiment of the present application, during the deposition process, the preset temperature range is 600°C to 900°C, the second preset time is 5 to 40 minutes, and the volume concentration in hydrogen is 5% to 900°C. Vertical graphene is prepared by using 100% methane gas as a carbon source, while changing the substrate temperature between 600°C and 900°C, and depositing vertical graphene for 5 to 40 minutes.
本申请一实施例中，将带有垂直石墨烯的石墨纸放置在磁控溅射仪器中溅射铂层，得到初级垂直石墨烯传感电极包括将带有垂直石墨烯的石墨纸放置于GVC-2000磁控溅射仪中，装配铂靶并连接氩气和氮气进行抽真空保持第三预设时间的磁控溅射。In one embodiment of the present application, placing graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode includes placing the graphite paper with vertical graphene in a GVC In the -2000 magnetron sputtering instrument, a platinum target is assembled and argon and nitrogen are connected to perform vacuuming and maintain magnetron sputtering for a third preset time.
当垂直石墨烯稳定生长在石墨纸之后，将制备好的垂直石墨烯放置在格微GVC-2000磁控溅射仪中，装配铂靶并连接上氩气和氮气后进行抽真空以及磁控溅射，得到初级垂直石墨烯传感电极。After the vertical graphene has stably grown on the graphite paper, the prepared vertical graphene is placed in the GVC-2000 magnetron sputtering instrument, a platinum target is assembled and connected to argon and nitrogen, followed by vacuuming and magnetron sputtering. irradiation to obtain primary vertical graphene sensing electrodes.
需要说明的是，本申请实施例中第三预设时间为10至15分钟，第三预设时间可以制备过程中的实际情况进行设置，本申请实施例对第三预设时间不作限制。It should be noted that in the embodiment of the present application, the third preset time is 10 to 15 minutes. The third preset time can be set according to the actual situation during the preparation process. The embodiment of the present application does not limit the third preset time.
在本申请的一些实施例中，在制备传感电极时，对于多巴胺传感电极和抗坏血酸传感传感电极，可以直接使用完成磁控溅射铂的垂直石墨烯进行对应的酶层叠加和选择性薄膜叠加，得到垂直石墨烯传感电极。而对于尿酸传感电极，将完成磁控溅射铂的垂直石墨烯作为工作电极连接电化学工作站以铂片电极作为对电极，银/氯化银作为参比电极。将三根电极浸入亚硫酸铂电镀液中，使用多步恒流法进行电化学沉积，具体地，第一阶段使用0.00006A的正向电流持续沉积10s，第二阶段以0.00006A的反向电流持续沉积10s，第三阶段以0.004A的反向电流持续沉积200s。沉积后取出电极，在室温下晾干超过2小时。将4wt％牛血清蛋白：2wt％戊二醛溶液：2wt％尿酸酶溶液按照5：2：1的配比混合制备成尿酸酶选择性薄膜，均匀滴涂2μl在铂表面，室温静置6～8小时，得到尿酸传感电极。In some embodiments of the present application, when preparing sensing electrodes, for dopamine sensing electrodes and ascorbic acid sensing electrodes, vertical graphene that has completed magnetron sputtering of platinum can be directly used for corresponding enzyme layer stacking and selection. The vertical graphene sensing electrodes are obtained by stacking the thin films. For the uric acid sensing electrode, the vertical graphene that has been magnetron sputtered with platinum is used as the working electrode and connected to the electrochemical workstation, with the platinum sheet electrode as the counter electrode and silver/silver chloride as the reference electrode. Three electrodes were immersed in the platinum sulfite plating solution, and electrochemical deposition was performed using a multi-step constant current method. Specifically, the first stage used a forward current of 0.00006A to continue deposition for 10 seconds, and the second stage used a reverse current of 0.00006A to continue deposition. Deposition was performed for 10 s, and the third stage continued deposition for 200 s with a reverse current of 0.004A. After deposition, remove the electrode and dry it at room temperature for more than 2 hours. Mix 4wt% bovine serum albumin: 2wt% glutaraldehyde solution: 2wt% uricase solution according to the ratio of 5:2:1 to prepare a uricase-selective film. Apply 2 μl evenly on the platinum surface and let it stand at room temperature for 6~ After 8 hours, the uric acid sensing electrode was obtained.
在本申请的一些实施例中，钾离子传感电极的制备过程包括将完成磁控溅射铂的垂直石墨烯作为工作电极连接电化学工作站以铂片电极作为对电极，银/氯化银作为参比电极；使用配置好的单体乙烯单体的聚合物(PEDOT)溶液，将三根电极浸入溶液中，使用多步恒流法进行电化学沉积，具体地，使用14μA的电流持续沉积400s。沉积后取出电极，在室温下晾干超过4小时。将2％w/w的缬氨霉素、0.5％w/w四苯硼钠、32.7％聚氯乙烯以及64.7％w/w癸二酸二异辛酯共200mg溶于700μL环己酮，并取2μl均匀滴涂在PEDOT层上，最后室温静置6～8小时，得到钾离子传感电极。In some embodiments of the present application, the preparation process of the potassium ion sensing electrode includes connecting the vertical graphene with magnetron sputtered platinum as the working electrode to the electrochemical workstation, using the platinum sheet electrode as the counter electrode, and silver/silver chloride as the counter electrode. Reference electrode: Use the configured polymer of ethylene monomer (PEDOT) solution, immerse the three electrodes in the solution, and use the multi-step constant current method to perform electrochemical deposition. Specifically, use a current of 14 μA to continue deposition for 400 seconds. After deposition, the electrode was taken out and allowed to dry at room temperature for more than 4 hours. Dissolve a total of 200 mg of 2% w/w valinomycin, 0.5% w/w sodium tetraphenylborate, 32.7% polyvinyl chloride and 64.7% w/w diisooctyl sebacate in 700 μL cyclohexanone, and Dispense 2 μl evenly on the PEDOT layer, and finally leave it at room temperature for 6 to 8 hours to obtain a potassium ion sensing electrode.
在本申请的一些实施例中，钙离子传感电极的制备过程包括将完成磁控溅射铂的垂直石墨烯作为工作电极连接电化学工作站以铂片电极作为对电极，银/氯化银作为参比电极；混合0.46％w/w钙离子载体、0.48％w/wNaTPB、33.02％PVC以及66.04％w/w的硝基苯辛醚共200mg于1mL的四氢呋喃中溶解，并取2μl均匀滴涂在PEDOT层上，最后室温静置6～8小时，得到钙离子传感电极。In some embodiments of the present application, the preparation process of the calcium ion sensing electrode includes connecting the vertical graphene with magnetron sputtered platinum as the working electrode to the electrochemical workstation, using the platinum sheet electrode as the counter electrode, and silver/silver chloride as the counter electrode. Reference electrode; mix 0.46% w/w calcium ionophore, 0.48% w/w NaTPB, 33.02% PVC and 66.04% w/w nitrophenyl ether, a total of 200 mg, dissolve in 1 mL of tetrahydrofuran, and apply 2 μl evenly On the PEDOT layer, finally leave it at room temperature for 6 to 8 hours to obtain a calcium ion sensing electrode.
在本申请的一些实施例中，钠离子传感电极的制备过程包括将完成磁控溅射铂的垂直石墨烯作为工作电极连接电化学工作站以铂片电极作为对电极，银/氯化银作为参比电极；在660ul的四氢呋喃中加入1％w/w的钠离子载体、65.45％w/w DOS、32.7％w/w PVC、0.55％w/w的四硼酸钠，共100mg，并充分地混合溶解，并取2μl均匀滴涂在PEDOT层上，最后室温静置6～8小时，得到钠离子传感电极。In some embodiments of the present application, the preparation process of the sodium ion sensing electrode includes connecting the vertical graphene with magnetron sputtered platinum as the working electrode to the electrochemical workstation, using the platinum sheet electrode as the counter electrode, and silver/silver chloride as the counter electrode. Reference electrode; add 1% w/w sodium ionophore, 65.45% w/w DOS, 32.7% w/w PVC, 0.55% w/w sodium tetraborate to 660ul of tetrahydrofuran, a total of 100mg, and fully Mix and dissolve, and apply 2 μl evenly on the PEDOT layer, and finally leave it at room temperature for 6 to 8 hours to obtain a sodium ion sensing electrode.
参照图7和图8，图7为垂直石墨烯的表面传感区域的扫描电镜表征图，图8为垂直石墨烯经过磁控溅射铂层的传感区域的扫描电镜表征图。可见，垂直石墨烯传感的传感区域分布均匀，使用离子体增强化学气相沉积、磁控溅射以及滴涂的方式制备得到的垂直石墨烯微传感电极有着良好电气性能；经过磁控溅射铂层后能够在保证不破坏原本的垂直石墨烯结构的前提下，覆盖一层均匀的纳米铂黑颗粒，进一步提升了该种材料的导电性，为酶层叠层的催化酶提供了良好的接触位点，从而提高了垂直石墨烯微传感电极的灵敏度和响应能力。Referring to Figures 7 and 8, Figure 7 is a SEM characterization of the surface sensing area of vertical graphene, and Figure 8 is a SEM characterization of the sensing area of vertical graphene after a magnetron sputtered platinum layer. It can be seen that the sensing area of vertical graphene sensing is evenly distributed. The vertical graphene micro-sensing electrode prepared by using ion-enhanced chemical vapor deposition, magnetron sputtering and drop coating has good electrical properties; after magnetron sputtering After the platinum layer is sprayed, it can be covered with a uniform layer of nano-platinum black particles without destroying the original vertical graphene structure, which further improves the conductivity of the material and provides a good catalytic enzyme for the enzyme layer stack. contact sites, thereby improving the sensitivity and responsiveness of vertical graphene micro-sensing electrodes.
以上是对本申请的较佳实施进行了具体说明，但本申请并不局限于上述实施方式，熟悉本领域的技术人员在不违背本申请精神的前提下还可作出种种的等同变形或替换，这些等同的变形或替换均包含在本申请权利要求所限定的范围内。The above is a detailed description of the preferred implementation of the present application, but the present application is not limited to the above-mentioned embodiments. Those skilled in the art can also make various equivalent modifications or substitutions without violating the spirit of the present application. Equivalent modifications or substitutions are included within the scope defined by the claims of this application.
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